Network polymers and methods of making and using same

ABSTRACT

The present invention relates to covalent adaptable networks (CANs) having exchangeable crosslinks which are able to undergo repeated covalent bond reshuffling through photo-activation at ambient temperatures. The invention provides covalent adaptable network forming compositions as well as methods of forming, remolding and recycling the CANs of the invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is divisional application of, and claimspriority under 35 U.S.C. § 121 to, U.S. application Ser. No. 16/326,567,filed Feb. 19, 2019, now allowed, which is a 35 U.S.C. § 371 nationalphase application of, and claims priority to, International ApplicationNo. PCT/US2017/048195, filed Aug. 23, 2017, which claims priority under35 U.S.C. § 119(e) to U.S. Provisional Patent Application No.62/378,447, filed Aug. 23, 2016, all of which applications areincorporated herein by reference in their entireties.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under Award Nos.W911NF-14-1-0605 awarded by the U.S. Army Research Office, DMR1310528awarded by the National Science Foundation, and 1000600740/W00057awarded by the National Science Foundation IUCRC. The government hascertain rights in the invention.

BACKGROUND OF THE INVENTION

Covalent adaptable networks (CANs) represent an effective strategy tocreate polymeric materials that retain certain useful properties ofcrosslinked networks, yet offer a route towards recycling and remoldingthrough covalent bond reshuffling reactions. In CANs with exchangeablecrosslinks, a chain end with an active site attacks a specific moiety onthe backbone of the polymer. A short-lived intermediate is formed, whichquickly breaks apart in one of several locations to regenerate theoriginal functionalities. The products of this exchange are chemicallyidentical to the original reactants, but directional stress within thenetwork drives the equilibrium towards a particular bond configurationto dissipate chain energy, which leads to macroscopic stress relaxationbehavior. Unlike an addition-based CAN, which involves a shiftingequilibrium that affects functional group conversion (as in aDiels-Alder network), an exchange-based CAN retains a constantcrosslinking density during bond rearrangement.

Several chemistries have been previously explored for adaptable networkpolymers, including thermally activated reactions such astransesterification, transamination, and disulfide exchange, as well aslight-triggered bond rearrangement using a reversibleaddition-fragmentation chain transfer (RAFT) mechanism.

Previous studies have taken advantage of light to instantaneouslyproduce thiyl or carbon centered radicals that are capable of additionto unsaturated species within the cross-link and statisticalfragmentation. Turning off the light results in rapid depletion of theradical concentration, thus, terminating the addition-fragmentationsequence. Although this method gives control over where (spatial) andwhen (temporal) plasticity is noted, issues such as inability to undergomultiple cycles, remold, flow in bulk, or yellowing/coloration of thematerial inherently limits the approach. Alternatively, scenarios whereheat acts as the stimulus utilize degenerate exchange reactions whichhave high kinetic barriers. Application of sufficient heat overcomesthese barriers and creates a distribution between reactants andproducts, cooling of these networks suppresses exchange. Typically,remoldability and multiple cycles are possible using thermally activatedsystems, however, spatial control is not inherently feasible, high heats(>120° C.) are required even with rubbery samples, and coloration of thematerial is often unavoidable.

There remains a need in the art for CANs that are capable of beingremolded, recycled and repaired at ambient temperatures withoutdegrading or discoloring the material. In certain embodiments, the CANsshould be fabricated using photo-, thermal-, or redox-initiationprocesses. In other embodiments, the covalent bond reshuffling should betriggered photolytically and/or thermally, wherein light and/or heat,respectively, can be used to activate or deactivate the bondreshuffling. In yet other embodiments, the covalent bond reshufflingshould be triggered with both spatial and temporal control. The presentinvention fulfills these needs.

BRIEF SUMMARY OF THE INVENTION

In one aspect, the invention provides compositions. In certainembodiments, the composition of the invention comprises at least onemultifunctional thioester containing monomer of Formula (I):

wherein in (I): A¹ and A² are each independently selected from the groupconsisting of optionally substituted C₁-C₁₅ alkylene, optionallysubstituted C₂-C₁₅ alkenylene, optionally substituted C₂-C₁₅ alkynylene,optionally substituted C₁₂-C₁₅ heteroalkylene, optionally substitutedC₂-C₁₅ heteroalkenylene and optionally substituted C₂-C₁₅heteroalkynylene; E¹ and E² are each independently selected from thegroup consisting of:

wherein each instance of Y¹ is independently selected from the groupconsisting of O and NR¹; and each instance of R¹ being independentlyselected from the group consisting of H and C₁-C₆ alkyl; m1 is 0 or 1;m2 is 0 or 1; X¹ is

wherein: bond a is to A¹, bond b is to E¹, Q is CH₂ or

and n is 0, 1, 2, 3, 4, 5 or 6; X² is

wherein: bond a is to A², bond b is to E², Q is CH₂ or

and n is 0, 1, 2, 3, 4, 5 or 6; each instance of Y² and Y³ isindependently selected from the group consisting of CR¹ ₂, O and NR¹;and each instance of R¹ is independently selected from the groupconsisting of H and C₁-C₆ alkyl. In certain embodiments, the compositionof the invention comprises at least one multifunctional thiol monomer.In certain embodiments, the composition of the invention comprises atleast one of a base and a nucleophile.

In certain embodiments, the at least one multifunctional thioestercontaining monomer is a monomer of Formula (Ia):

In certain embodiments, the at least one multifunctional thioestercontaining monomer is selected from the group consisting of: allyl4-((3-(allyloxy)-3-oxopropyl)thio)-4-oxobutanoate; S-(2-isocyanatoethyl)3-isocyanatopropanethioate; S-(2-(((allyloxy)carbonyl)amino)ethyl)3-(((allyloxy)carbonyl)amino)propanethioate; S-(2-(3-allylureido)ethyl)3-(3-allylureido)propanethioate;S-(2-(((oxiran-2-ylmethoxy)carbonyl)amino)ethyl)3-(((oxiran-2-ylmethoxy)carbonyl)amino)propanethioate;S-(2-(3-allyl-3-(tert-butyl)ureido)ethyl)3-(3-allyl-3-(tert-butyl)ureido)propanethioate;4,9,13-trioxo-3,14-dioxa-8-thia-5,12-diazahexadecane-1,16-diyldiacrylate;4,9,13-trioxo-3,14-dioxa-8-thia-5,12-diazahexadecane-1,16-diylbis(2-methylacrylate); 2-(acryloyloxy)ethyl4-((3-(2-(acryloyloxy)ethoxy)-3-oxopropyl)thio)-4-oxobutanoate;2-(methacryloyloxy)ethyl4-((3-(2-(methacryloyloxy)ethoxy)-3-oxopropyl)thio)-4-oxobutanoate;

wherein m is 0, 1, 2, 3, 4, 5 or 6.

In certain embodiments, the at least one multifunctional thiol monomeris selected from the group consisting of:

wherein each instance of n is independently an integer from 0 to 500.

In certain embodiments, the at least one multifunctional thiol monomeris selected from the group consisting of: pentaerythritoltetramercaptopropionate (PETMP); ethylene glycolbis(3-mercaptopropionate) (EGBMP); trimethylolpropanetris(3-mercaptopropionatexTMPMP); 2,4,6-trioxo-1,3,5-triazina-triy(triethyl-tris (3-mercapto propionate); 1,2-ethanedithiol;1,3-propanedithiol; 1,4-butanedithiol; 1,5-pentanedithiol;1,6-hexanedithiol; 1,8-octanedithiol; 1,9-nonanedithiol;1,11-undecanedithiol; 1,16-hexadecanedithiol;2,5-dimercaptomethyl-1,4-dithiane; pentaerythritol tetramercaptoacetate;trimethylolpropane trimercaptoacetate; glycol dimercaptoacetate;2,3-dimercapto-1-propanol; DL-dithiothreitol; 2-mercaptoethylsulfide;2,3-(dimercaptoethylthio)-1-mercaptopropane; 1,2,3-trimercaptopropane;toluenedithiol; benzenedithiol; biphenyldithiol; benzenedimethanethiol;xylylenedithiol; 4,4′-dimercaptostilbene; and glycoldimercaptopropionate.

In certain embodiments, the base is capable of deprotonating at leastabout 10% of the thiol groups in the multifunctional thiol monomers. Inother embodiments, the base has a conjugate acid with a pKa from about 2to about 15. In yet other embodiments, the base is capable ofdeprotonating at least about 10% of the thiol groups in the composition.In yet other embodiments, the base is selected from the group consistingof an alkylthiolate salt, tetramethylguanidine (TMG),1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU), N,N-Diisopropylethylamine(DIPEA or Hunig's base), 4-tert-butyl pyridine, triethylamine (TEA), andN,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA).

In certain embodiments, the nucleophile has a nucleophilicity value (N)greater than about 10. In other embodiments, the nucleophile is selectedfrom the group consisting of quinuclidine, 1,4-diazabicyclo[2.2.2]octane(DABCO), 4-Dimethylaminopyridine (DMAP), IMes, IPr, Ender's carbene,PPh₃ P(nBu)₃, P(tBu)₃, PCy₃, and PMe₃.

In certain embodiments, the composition further comprises at least onepolymerization initiator selected from the group consisting of aphotoinitiator, a thermal initiator and a redox initiator.

In certain embodiments, the at least one photoinitiator is activatedupon exposure to light in the IR range, visible range, and/or UV range.In yet other embodiments, the at least one photoinitiator is selectedfrom the group consisting of: acetophenone, benzophenone,2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone,Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone,2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one,Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Ethyl(2,4,6-trimethylbenzoyl) phenyl phosphinate, lithiumphenyl-2,4,6-trimethylbenzoylphosphinate,

In certain embodiments, the at least one thermal initiator is reactiveupon exposure to temperatures of about 30° C. to about 200° C. In yetother embodiments, the at least one thermal initiator is a compoundselected from the group consisting of tert-Amyl peroxybenzoate,4,4-Azobis(4-cyanovaleric acid), 1,1′-Azobis(cyclohexanecarbonitrile),2,2′-Azobisisobutyronitrile (AIBN), Benzoyl peroxide,2,2-Bis(tert-butylperoxy)butane, 1,1-Bis(tert-butylperoxy) cyclohexane,2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane,2,5-Bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,Bis(1-(tert-butylperoxy)-1-methylethyl)benzene,1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-Butylhydroperoxide, tert-Butyl peracetate, tert-Butyl peroxide, tert-Butylperoxybenzoate, tert-Butylperoxy isopropyl carbonate, cumenehydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroylperoxide, 2,4-pentanedione peroxide, peracetic acid and potassiumpersulfate.

In certain embodiments, the at least one redox initiator is one or morecompounds selected from the group consisting of: sodium iodide/hydrogenperoxide, potassium iodide/hydrogen peroxide, benzoylperoxide/dimethyaniline, benzoyl peroxide/N,N-dimethyl p-toluidine,benzoyl peroxide/4-N,N-dimethylaminophenethyl alcohol, benzoylperoxide/ethyl 4-dimethylaminobenzoate, glucose oxidase/oxygen/iron(II)sulfate and copper(II) sulfate/sodium ascorbate.

In certain embodiments, the relative ratio between the at least onemultifunctional thioester containing monomer and the at least onemultifunctional thiol monomer in a such that the total number of thiolfunctionalities present on the at least one multifunctional thiolmonomer within the composition is greater than the total number of E¹and E² functionalities present on the at least one multifunctionalthioester containing monomer.

In certain embodiments, the base is selected from the group consistingof a photo-activatable base and a thermal-activatable base.

In certain embodiments, the photo-activatable base is a compoundselected from the group consisting of:

1,2-Diisopropyl-3-[Bis(dimethylamino) methylene]guanidium2-(3-benzoylphenyl)propionate,1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate,and(Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminiumtetrakis(3-fluorophenyl)borate.

In certain embodiments, the base is a thermal-activatable base selectedfrom the group consisting of:

In certain embodiments, the composition further comprises an acidselected from the group consisting of a photo-activatable acid and athermal-activatable acid. In other embodiments, the photo-activatableacid is a compound selected from the group consisting of:

Bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate,Bis(4-tert-butylphenyl)iodonium p-toluenesulfonate,Bis(4-tert-butylphenyl)iodonium, Boc-methoxyphenyldiphenylsulfoniumtriflate, (4-tert-Butylphenyl)diphenylsulfonium triflate,Diphenyliodonium hexafluorophosphate, Diphenyliodonium nitrate,Diphenyliodonium perfluoro-1-butanesulfonate, Diphenyliodoniump-toluenesulfonate, Diphenyliodonium triflate,(4-Fluorophenyl)diphenylsulfonium triflate, N-Hydroxynaphthalimidetriflate, N-Hydroxy-5-norbornene-2,3-dicarboximideperfluoro-1-butanesulfonate, (4-Iodophenyl)diphenylsulfonium triflate,(4-Methoxyphenyl)diphenylsulfonium triflate, 2-(4-Methoxystyryl)-4,6-bis(trichloro methyl)-1,3,5-triazine, (4-Methylphenyl)diphenylsulfoniumtriflate, (4-Methylthio phenyl) methylphenyl sulfonium triflate,(4-Phenoxyphenyl)diphenylsulfonium triflate, (4-Phenylthiophenyl)diphenylsulfonium triflate, Triarylsulfonium hexafluorophosphatesalts, Triphenyl sulfonium perfluoro-1-butanesufonate,Triphenylsulfonium triflate, Tris(4-tert-butylphenyl) sulfoniumperfluoro-1-butanesulfonate, and Tris(4-tert-butylphenyl)sulfoniumtriflate.

In other embodiments, the thermal-activatable acid selected from thegroup consisting of:

In certain embodiments, the monomers undergo at least partialpolymerization to form a covalent adaptable network (CAN) polymer. Inother embodiments, the CAN comprising an activatable base does notexhibit significant bond exchange before activation of the base. In yetother embodiments, the CAN comprising an activatable base exhibits bondexchange after activation of the base. In other embodiments, the CANcomprising an activatable acid exhibits bond exchange before activationof the acid. In yet other embodiments, the CAN comprising an activatablebase does not exhibit significant bond exchange after activation of theacid.

The invention further provides a composition comprising a cross-linkedCAN polymer comprising a plurality of thioester linkages and a pluralityof free thiol groups, and further comprising at least one exchangecatalyst selected from a base and a nucleophile.

In certain embodiments, the at least one exchange catalyst is covalentlybound to the CAN polymer. In other embodiments, the at least oneexchange catalyst is not covalently bound to the CAN polymer.

In certain embodiments, the base is capable of deprotonating at leastabout 10% of the free thiol groups in the CAN. In other embodiments, thenucleophile has a nucleophilicity value (N) greater than about 10.

In certain embodiments, the CAN is formed through one or more processesselected from the group consisting of thiol-ene polymerization,thiol-alkyne polymerization, thiol-acrylate polymerization,thiol-methacrylate, acrylate polymerization, methacrylatepolymerization, styrene polymerization, alcohol-isocyanatepolymerization, thiol-isocyanate polymerization, thiol-epoxidepolymerization, thiol-isothiocyanate polymerization, thiol-halidepolymerization, thiol-malemide, thiol-activated ester polymerization,copper-catalyzed azide alkyne polymerization, strain-promoted azidealkyne polymerization, and epoxide-carboxylic acid polymerization.

In certain embodiments, the polymer network undergoes bond exchangethrough nucleophilic attack on the thioester linkages by the free thiolgroups.

In certain embodiments, the polymer exhibits plasticity. In otherembodiments, the polymer can be reshaped after polymerization. In yetother embodiments, the polymer is capable of alleviating polymerizationinduced stress.

In certain embodiments, the base is selected from the group consistingof a photo-activatable base and a thermal-activatable base. In otherembodiments, the photo-activatable base is a compound selected from thegroup consisting of:

1,2-Diisopropyl-3-[Bis(dimethylamino)methylene]guanidium2-(3-benzoylphenyl)propionate,1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate,and(Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminiumtetrakis(3-fluorophenyl)borate.

In other embodiments, the base is a thermal-activatable base selectedfrom the group consisting of:

In certain embodiments, the CAN does not exhibit significant bondexchange before activation of the base. In other embodiments, the CANexhibits bond exchange after activation of the base.

In certain embodiments, the CAN further comprises an acid selected fromthe group consisting of a photo-activatable acid and athermal-activatable acid. In other embodiments, the photo-activatableacid is a compound selected from the group consisting of:

Bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate,Bis(4-tert-butylphenyl)iodonium p-toluenesulfonate,Bis(4-tert-butylphenyl)iodonium, Boc-methoxyphenyldiphenylsulfoniumtriflate, (4-tert-Butylphenyl)diphenylsulfonium triflate,Diphenyliodonium hexafluorophosphate, Diphenyliodonium nitrate,Diphenyliodonium perfluoro-1-butanesulfonate, Diphenyliodoniump-toluenesulfonate, Diphenyliodonium triflate,(4-Fluorophenyl)diphenylsulfonium triflate, N-Hydroxynaphthalimidetriflate, N-Hydroxy-5-norbornene-2,3-dicarboximideperfluoro-1-butanesulfonate, (4-Iodophenyl)diphenylsulfonium triflate,(4-Methoxyphenyl)diphenylsulfonium triflate,2-(4-Methoxystyryl)-4,6-bis(trichloro methyl)-1,3,5-triazine,(4-Methylphenyl)diphenylsulfonium triflate, (4-Methylthiophenyl)methylphenyl sulfonium triflate, (4-Phenoxyphenyl)diphenylsulfonium triflate,(4-Phenylthiophenyl) diphenylsulfonium triflate, Triarylsulfoniumhexafluorophosphate salts, Triphenylsulfoniumperfluoro-1-butanesufonate, Triphenylsulfonium triflate,Tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate, andTris(4-tert-butylphenyl)sulfonium triflate.

In other embodiments, the thermal-activatable acid is selected from thegroup consisting of:

In certain embodiments, the CAN exhibits bond exchange before activationof the acid. In other embodiments, the CAN does not exhibit significantbond exchange after activation of the acid.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of illustrating the invention, there are depicted in thedrawings certain embodiments of the invention. However, the invention isnot limited to the precise arrangements and instrumentalities of theembodiments depicted in the drawings.

FIG. 1A is a diagram of the conceptual overview of stress relaxation inmacroscopic networks via thiol-thioester exchange. When free thiolgroups and a catalyst capable of creating a concentration of thiolateare present, exchange reactions occur continuously without externalintervention at ambient temperature. FIG. 1B is a simplifiedrepresentation of mechanisms for the thiol-thioester exchange catalyzedby bases (top pathway) and nucleophiles (bottom pathway).

FIG. 2 is set of structures of exemplary ene and thiol monomers of theinvention (TEDAE and PETMP, respectively), the base PMDETA, andinitiator DMPA.

FIG. 3 is a graph of a DMA curve of a thioester-containing elastomer,showing tensile storage modulus (solid line) and tan delta (dashed line)as a function of temperature. The film was made with TEDAE, PETMP, a 2:1ratio of thiol and ene groups, and 0.05 equivalents of PMDETA per thiolgroup. The glass transition temperature was measured as the peak of thetan delta curve at −19° C., and the rubbery modulus was measured at 20°C. as 1 MPa.

FIG. 4 is a graph of rheometer time sweep data, monitoring the thiol-enepolymerization in the presence of various base catalysts. The shearstorage modulus (closed symbols) and loss modulus (open symbols) wererecorded over time, using a strain of 5% and frequency of 5 rad/s. Thesamples were exposed to light at t≥60 s (indicated by a dashed line),using a 365 nm filter and light intensity of 3 mW/cm². The resin mixturecontained PETMP, TEDAE, 2:1 thiol:ene, and either no catalyst or 0.05equivalents of TEA, PMDETA, or DBU per thiol. While samples containingno base, TEA, or PMDETA, reached a final modulus after seconds ofirradiation time, the sample containing DBU took nearly 50 minutes toreach a similar storage modulus as the others.

FIG. 5 is a graph showing results of creep experiments performed atambient temperature, using one experimental and three controlconditions. The complete formulation included PETMP, TEDAE, 2:1 ratio ofthiol:ene groups, and 0.05 equivalents PMDETA per thiol group. Controlformulations included absence of excess thiol, absence of base, andabsence of thioester.

FIG. 6 is a set of schemes and calculated values of activation energyand enthalpy that show that the degenerate exchange of protonatedalcohols or thiols with their ester analogs have very high kineticbarriers (top), whereas their deprotonated counterparts have very lowkinetic barriers (middle). Evidently the thiol-thioester exchange occursrapidly with mild organic base (such a TEA) due to the significantlylower pKa of thiols when compared to similar alcohols (bottom).Calculations were performed with Gaussian 09 computational chemistrypackage, using Trestles Supercomputer, XSEDE.

FIG. 7 is a graph of normalized tensile stress relaxation experimentswithout a base catalyst, using a fully-polymerized film with 2:1thiol:ene groups, performed at 24° C. and 124° C. The formulationcontained PETMP, TEDAE, and no base catalyst, and the samples were runat 4% strain while monitoring stress over time.

FIGS. 8A-8B are graphs showing the relationship of base concentrationand stress relaxation. Increasing the concentration of PMDETA in thenetwork increased the rate of stress relaxation (constant applied strainof 10%, FIG. 8A). A first order dependence of the base is noted in thissystem based on the normalized stress for each condition at t=15 min(FIG. 8B). General formulations: TEDAE (1.00 equiv), PETMP (1.00 equiv),PMEDTA (0.00 mol % [square], 8.00 mol % [circle], 16.0 mol % [uptriangle], 24.0 mol % [down triangle], 32.0 mol % [diamond]), and DMPA(1.00 mol %).

FIG. 9 is a graph showing frequency sweeps in shear of fully-curedsamples; shown are the storage moduli (closed symbols) and loss moduli(open symbols) over four decades of frequency at 5% rotational strain.The following base catalysts, loaded at 0.05 molar equivalents perthiol, were studied: control with no base (square), TEA (left triangle),PMDETA (right triangle), and DBU (star).

FIGS. 10A-10D are graphs and diagrams of nanoimprint lithography on athioester-containing elastomer. The master silicon pattern had a depthof 220 nm and period of 880 nm. Imprinting was performed at 20 barpressure for 10 minutes close to ambient temperature. FIG. 10A is asurface profile of the imprinted surface over time, continuouslymonitored by contact AFM and analyzed at various time points. FIG. 10Bis a graph of the imprinted pattern height changes against elapsed timeafter imprinting. FIG. 10C is a 10×10 μm area topography of theimprinted surface. Surface defects are due to defects in the siliconmaster. FIG. 10D is a set of photographs demonstrating changes in theoptical reflective properties of the film over time after imprinting.After 24 hours, the surface pattern had faded to the point where coloredreflection was no longer visible at the same viewing angle.

FIG. 11 is a diagram demonstrating the concept for a “ON” and “OFF”switch to control plasticity in a cross-linked network polymer.

FIGS. 12A-12C are graphs and images demonstrating the dynamic behaviorof the “ON/OFF” switches of the invention. FIG. 12A is a graph of apartial cure experiment with a stoichiometric thiol-ene resin, includingstress relaxation of various conditions and a nanoimprint lithographydemonstration. In films where the second stage light exposure wasperformed through a photomask, the areas that were not exposed to lightretained thiols to undergo bond rearrangement; in irradiated areas,remaining free thiols were completely consumed. FIG. 12B shows thatnanoimprint lithography on the entire film surface, followed by afloodcure, resulted in a colored reflection only in unexposed regions.Scale bar on photographic image is 5 mm; scale bar on optical micrographinset is 100 μm. FIG. 12C is a graph showing a demonstration of aphotoprotected base as an on-switch for bond rearrangement within thenetwork. A creep experiment revealed that the network behaved as atypical crosslinked elastomer until it was exposed to low-wavelength UVlight, which caused the release of the base TMG within the network.

FIG. 13 is a scheme of a representative procedure for the preparation ofa thioester containing network polymer via a photoinitiated thiol-enereaction.

FIG. 14A is a graph of kinetics of the thiol-ene reaction with athioester containing diene. General reaction conditions: TEDAE (1.00equiv), PETMP (1.00 equiv), PMDETA (10.0 mol %), and DMPA (2.00 mol %)monitored by in situ IR. Light on at 60.0 seconds and continuouslyirradiated; 365 nm LED (50.0 mW/cm²). FIG. 14B is a set of graphs ofdifferent thiol-ene formulations, which show that varying amounts ofthiol can remain unreacted in the network based on initialstoichiometry. General reaction conditions: TEDAE (1.00 equiv [100% xsthiol], 1.50 equiv [50.0% xs thiol], or 2.00 equiv [0.00% xs thiol]),PETMP (1.00 equiv), PMDETA (10.0 mol %), and DMPA (2.00 mol %) monitoredby in situ IR. Light on at 60.0 seconds and continuously irradiated; 365nm LED (50.0 mW/cm²).

FIGS. 15A-15B are a scheme and graph showing that tethering the base tothe network evidently does not affect the rate of relaxation whencompared to the free base (constant applied strain of 10%). Generalformulation: 1) blue line—TEDAE (1.00 equiv), PETMP (1.00 equiv), PMDETA(10.0 mol %), DMPA (2.00 mol %); 2) grey line—TEDAE (1.00 equiv), PETMP(1.00 equiv), PMDETA-ene (10.0 mol %), DMPA (2.00 mol %). Although thetethered base gave slightly faster kinetics, the difference is minimal.

FIG. 16 is a graph showing that increasing the temperature accordinglyincreases the rate of stress relaxation with basic catalysts; stressrelaxation (constant applied strain of 10%) experiment performed at 25°C., 50° C., and 75° C. Higher crosslink densities were utilized forthese experiments. General formulation: TEDAE (1.50 equiv), PETMP (1.00equiv), PMDETA (10.0 mol %), and DMPA (2.00 mol %).

FIG. 17A is a graph comparing samples with base relax stress whenstrained (0.75 and 0.10 mm/min) and samples without base quickly buildup stress (0.75 and 0.10 mm/min). When slower strain rates (0.10 mm/min)were applied, no stress was built up. General formulation: TEDAE (1.00equiv), PETMP (1.00 equiv), PMDETA (0.00 mol % or 10.0 mol %), and DMPA(2.00 mol %). FIG. 17B is a graph showing that increasing thetemperature slightly increases the rate of stress relaxation withnucleophilic catalysts; stress relaxation at 25° C., 50° C., and 75° C.,10% strain. Higher crosslink densities were utilized for theseexperiments; also, DMAP was used as other nucleophiles, such asquinuclidine, were found to sublime out of the polymer at higher heats.General formulation: TEDAE (1.50 equiv), PETMP (1.00 equiv), DMAP (10.0mol %), and DMPA (2.00 mol %).

FIGS. 18A-18D are a set of images showing a representative procedure forthe formation of a plano-convex lens from recycled polymer. FIG. 18Adepicts the formation of the original lense. FIG. 18B is a set of imagesshowing the lens depicted in FIG. 18A being cut. FIG. 18C is a set ofimages showing the compression and reformation of the cut polymericmaterial. FIG. 18D is an image of the reformed lens.

FIG. 19A is a graph showing that increasing the pKa of the organic basein the network accordingly increases the rate of stress relaxation(constant applied strain of 10%). General formulations: TEDAE (1.00equiv), PETMP (1.00 equiv), organic base (3.00 mol %), and DMPA (2.00mol %). FIG. 19B is a graph showing that increasing the nucleophilicityof the catalyst in the network accordingly increases the rate of stressrelaxation (constant applied strain of 10%). General formulations: TEDAE(1.00 equiv), PETMP (1.00 equiv), nucleophilic catalyst (3.00 mol %),and DMPA (2.00 mol %). All nucleophilicity values taken from Baidya, etal., 2007, Angew. Chem. Int. Ed. 46:6176, and are values obtained inMeCN.

FIG. 20A is a graph of the creep compliance showing the requirement forfree thiol, thioester, and nucleophile in the network forrearrangement/relaxation/remolding to occur. General formulations: allcomponents (top line)-TEDAE (1.00 equiv), PETMP (1.00 equiv),quinuclidine (5.00 mol %), and DMPA (2.00 mol %); w/o thiol (bottomline)—TEDAE (1.00 equiv), PETMP (0.25 equiv), quinuclidine (5.00 mol %),and DMPA (2.00 mol %); w/o thioester (second from bottom line)-DAEC(1.00 equiv), PETMP (1.00 equiv), quinulicidine (5.00 mol %), and DMPA(2.00 mol %); w/o base (second from top line)—TEDAE (1.00 equiv), PETMP(1.00 equiv), and DMPA (2.00 mol %).

FIG. 20B is a graph comparing the rate of stress relaxation of networkscontaining no catalyst (green), quinuclidine (blue), and TMG (red)(constant applied strain of 10%). General formulations: TEDAE (1.00equiv), PETMP (1.00 equiv), amine catalyst (0.00 mol % or 3.00 mol %),and DMPA (2.00 mol %).

FIG. 21 is a scheme showing the photorelease of the base,tetramethylguanidine, which serves as a photoactivatable “ON” switch.

FIGS. 22A-22B are schemes of an exemplary thiol-ene formulationcomprising the photoactivatable base.

FIG. 23 is a graph showing the kinetics of the thiol-ene reactionbetween TEDAE and PETMP in the presence of varying amounts of DBU (0.00mol %, 3.00 mol %, and 10.0 mol %) showing significant inhibition of thethiol-ene reaction at higher concentrations of DBU. General reactionconditions: TEDAE (1.00 equiv), PETMP (1.00 equiv), DBU (0.00 mol %,3.00 mol %, or 10.0 mol %), and DMPA (2.00 mol %) monitored by in situIR. Light on at 60.0 seconds and continuously irradiated; 365 nm LED(50.0 mW/cm²).

FIG. 24A is a graph showing photoinitiated stress relaxation in anetwork polymer with temporal control (10% strain, light on at 5, 10,and 15 minutes, continuously irradiated, 365 nm, 75 mW/cm²). Line attop-not irradiated control. FIG. 24B is a graph showing temporal controlover mechanical properties of a network polymer (0.25 mm/min, light onat 6, 12, and 20% strain, continuously irradiated, 365 nm, 75 mW/cm²).Upward sloping line-not irradiated control (yielded at ˜26% strain).

FIG. 25 is a set of images of the dynamic mechanical analysis setup usedto analyze the network polymers comprising the photoactivatablebase/“ON” switch.

FIG. 26 is a scheme showing the photorelease of phenylacetic acid, whichserves as a photoactivatable “OFF” switch, deactivating the base presentwithin the network polymer.

FIGS. 27A-27B are schemes of an exemplary thiol-ene formulationcomprising the photoactivatable acid.

FIG. 28 is a graph showing the kinetics of the thiol-ene reactionbetween TEDAE and PETMP in the presence of varying amounts ofquinuclidine (0.00 mol %, 3.00 mol %, and 10.0 mol %) showing noinhibition of the thiol-ene reaction. General reaction conditions: TEDAE(1.00 equiv), PETMP (1.00 equiv), quinuclidine (0.00 mol %, 3.00 mol %,or 10.0 mol %), and DMPA (2.00 mol %) monitored by in situ IR. Light onat 60.0 seconds and continuously irradiated; 365 nm LED (50.0 mW/cm²).

FIG. 29 is a graph showing that increasing the concentration ofquinuclidine in the network accordingly increases the rate of stressrelaxation (constant applied strain of 10%, left). A first orderdependence of the nucleophile is noted in this system based on thenormalized stress for each condition at t=15 min (right). Generalformulations: TEDAE (1.00 equiv), PETMP (1.00 equiv), quinuclidine (0.00mol % [top], 0.50 mol % [second from top], 1.00 mol % [third from top],3.00 mol % [fourth from top], 6.00 mol % [curved bottom line]), and DMPA(2.00 mol %).

FIG. 30 is a graph of a time-course over 5 minutes (300 sec) for thephoto-triggered released of phenylacetic acid from PA by ¹H-NMR. Generalreaction conditions: PA (1.00 equiv), 1,3,5-trimethoxybenzene (0.50equiv, internal standard), MeCN-d₃ (0.10 M), —75.0 mW/cm², 365 nm, RT.

FIG. 31A is a graph showing photoinitiated fixation in a network polymerwith temporal control (10% strain, light on at 5 [top], 20 [second fromtop], and 120 [third from top] seconds, irradiated for 120 seconds,320-500 nm, 75 mW/cm², a small thermal recovery was noted in each caseafter the light was turned off). Curved bottom line-not irradiatedcontrol. FIG. 31B is a graph showing temporal control over mechanicalproperties of a network polymer (0.25 mm/min, light on at 25 [left], 50[middle], and 75% [right] strain, irradiated continuously, 320-500 nm,75 mW/cm²). Downward sloping line-not irradiated control.

FIG. 32 is a set of images of the dynamic mechanical analysis setup usedto analyze the network polymers comprising the photoactivatableacid/“OFF” switch.

FIGS. 33A-33B are images of swelling and depolymerization tests atambient temperature. Four thioester-containing samples and one controlsample were prepared, using TEDAE or DVE-3, respectively, as the dienemonomer. The 250 μm thick films did not contain any base catalyst aspolymerized. Thioester-containing films were each suspended in a vialcontaining one of the following stirred solutions: ethanol (1a),mercaptoethanol (1b), ethanol with 5 wt % TEA (2a), and mercaptoethanolwith 5 wt % TEA (2b). The control film was suspended in a separate vialcontaining mercaptoethanol and 5 wt % TEA (3b). Within seconds, thethioester-containing film had depolymerized and dissolved completely invial 2b, while the films remained intact under all other testedconditions. Conditions 1b and 3b caused the films to swell, but nopolymerization was observed even after 24 hours soaking time, due to theabsence of base catalyst (1b) or the absence of thioester (3b).

FIG. 34 is a reaction scheme for recycling and repolymerizingcrosslinked photopolymers by both radical-mediated thiol-ene andanion-mediated thiol-thioester exchange reactions. In particular, thepristine polymer is originally prepared by photo-induced thiol-enepolymerization between stoichiometric tetra-thiol andthioester-containing diallyl ethers. The bulk photopolymer is degradedinto thiol oligomers, by exchanging with a specific amount oftetra-thiols under basic condition. Subsequently, these oligomers arepolymerized with thioester-containing diallyl ether by thiol-enereaction. Three representative complete cycles are demonstrated here toindicate the capacity for full property recovery.

FIG. 35A is a graph of dynamic mechanical analysis (DMA) of pristinePETMP-TEDAE polymer, and reclaimed polymers from oligomer 2 (Table 1)and TEVAE. The glass transition temperature occurs at −2° C., and therubbery modulus is 6 MPa. FIG. 35B is a graph of tensile stress-straincurves of pristine PETMP and TEDAE polymer, and reclaimed polymer fromoligomer 2 (Table 1) and stoichiometric TEDAE. FIG. 35C is a graphcomparing transparency of pristine and recycled PETMP-TEDAEphotopolymers. Film thickness is 0.25 mm.

FIG. 36 Fourier transform infrared spectra of the pristine PETMP-TEDAEmonomer mixture, pristine polymer and degraded oligomer (stoichiometricnumber of 0.125, oligomer 2 from Table 1).

FIG. 37A is a set of ¹H NMR spectra of recycled oligomer 1 (Table 1) forvarious cycles. Oligomer was obtained by degrading in excess PETMP witha stoichiometric number of 0.167 in acetone with catalytic amount ofTEA, and then dried under vacuum. FIG. 37B is a graph of a number gelpermeation chromatography profiles of oligomer 2 (Table 1) at variousrounds of recycling. Oligomer was obtained by degrading in excess PETMPwith a stoichiometric number of 0.125 in acetone with catalytic amountof TEA, and then dried under vacuum.

FIG. 38 is a graph of reaction kinetics profiles of stoichiometricthiol-ene polymerization for pristine PETMP-TEDAE, as well as variousoligomers with TEDAE. Formulations of oligomers are listed in Table 1.Irradiation conditions: 1 mol % DMPA to thiol or alkene groups, 5mW/cm²@365 nm, light turned on at 30 sec. The thiol peak centered at2570 cm⁻¹ was used to determine reaction conversions.

FIG. 39 is a graph of thermogravimetric analysis of pristine PETMP-TEDAEand PETMP-diallyl adipate. The samples were ramped at 10° C./min underN₂.

FIG. 40 is a set of structures of exemplary monomers of the invention.Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP);trimethylolpropane tris(3-mercaptopropionate) (TMPTMP);dipentaerythritol hexa(3-mercaptopropionate) (Di-PETMP);ethoxilated-trimethylolpropan tri(3-Mercaptopropionate) (ETTMP 700 andETTMP 1300); polycaprolactone tetra(3-mercaptopropionate) (PCL4MP);diallyl adipate; thioester containing diallyl ether (TEDAE); thioestercontaining diisocyanate (TEDI); disulfide diallyl ether (DSDAE).

FIG. 41 is a set of ¹H NMR spectra of oligomers recycled from polymersprepared by various thiol monomers and TEDAE. (1) TMPTMP; (2) ETTMP 700;(3) ETTMP 1300; (4) TEMPIC; (5) PCL4MP; (6) Di-PETMP. The stoichiometricratio between thiols and thioesters used for recycling are listed inTable 3.

FIG. 42 is a graph of the reaction kinetics of monomer conversionbetween stoichiometric PETMP and TEDI. 1 mol % Irgacure 907 instoichiometric PETMP-TEDI. Irradiation conditions: 5 mW/cm⁻² with 365 nmfilter. The light was turned on at 1 min.

FIG. 43 is an FT-IR spectra of the polythiourethane prepared fromstoichiometric reaction of PETMP and TEDI. (A) Stoichiometric monomermixture; (B) Polymer cured after 10 min irradiation under 5 mW/cm⁻²@365nm at ambient; (C) Polymer post-cured at 80° C. overnight. 1 mol %Irgacure 907 was used as initiator.

FIG. 44 is a dynamic mechanical analysis of pristine PETMP-TEDI andrecycled polythiourethane. The glass transition temperature isapproximately 74° C., and the rubbery modulus is approximately 9 MPa.

FIG. 45 is a set of stress-strain curves of polythiourethane preparedfrom stoichiometric PETMP and TEDI, as well as the reclaimed polymerprepared from oligomer (isocyanate/thiol stoichiometric number of 0.125)and TEDI. 63.5 mm×9.5 mm×0.25 mm dogbone samples were straining at 0.75mm/min at ambient.

FIG. 46 is a dynamic mechanical analysis of pristine and recycledPETMP-DSDAE. The glass transition temperature is about −6° C., and therubbery modulus is about 9 MPa.

FIG. 47 is a graph of the reaction kinetics of disulfide polymer betweenstoichiometric PETMP and DSDAE. 1 mol % Irgacure 184 in stoichiometricPETMP-DSDAE. Irradiation conditions: 10 mW/cm⁻² with 365 nm filter. Thelight was turned on at 1 min.

FIG. 48 is a thermogravimetric analysis of composite thioester polymerswith various particle loadings. The samples were ramped at 10° C./minunder N₂.

FIG. 49 is a dynamic mechanical analysis of composite thioesterphotopolymers. 50 wt % and 60 wt % silica particles were polymerized inPETMP-TEDAE matrix, with 1 mol % DMPA with respect to monomers.

FIGS. 50A-50B are a set of images of contact liquid photolithography ofpristine (FIG. 50A) and recycled (FIG. 50B) PETMP-TEDAE polymers. Bothpristine and recycled samples consist of stoichiometric PETMP-TEDAEmonomers with 0.5 wt % 1184 and 0.3 wt % methylhydroquinone withrespective to polymerizable components. Photomasks are with 100 μmcircles separated by 100 μm screening gaps. Collimated UV light (50mW/cm² @365 nm) is shown on pristine samples for 120 sec, while onrecycled samples for 80 sec.

FIG. 51 is a graph showing polymerization induced stress measured for athioester network (bottom line) comprising TEDAE (1.0 eq), PETMP (1.1eq) and TMG (0.03 eq) and a control polymer network (top line)comprising DAEC (1.0 eq), PETMP (1.1 eq) and TMG (0.03 eq).

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the unexpected discovery of covalentadaptable networks (CANs) that have exchangeable crosslinks and are ableto undergo repeated covalent bond reshuffling at ambient temperatures.The invention provides CAN-forming compositions as well as methods offorming, remolding and recycling the CANs of the invention.

Definitions

As used herein, each of the following terms has the meaning associatedwith it in this section.

Unless defined otherwise, all technical and scientific terms used hereingenerally have the same meaning as commonly understood by one ofordinary skill in the art to which this invention belongs. Generally,the nomenclature used herein and the laboratory procedures in cellculture, molecular genetics, and organic chemistry are those well-knownand commonly employed in the art.

As used herein, the articles “a” and “an” refer to one or to more thanone (i.e. to at least one) of the grammatical object of the article. Byway of example, “an element” means one element or more than one element.

As used herein, the term “about” will be understood by persons ofordinary skill in the art and will vary to some extent on the context inwhich it is used. As used herein when referring to a measurable valuesuch as an amount, a concentration, a temporal duration, and the like,the term “about” is meant to encompass variations of ±20% or ±10%, morepreferably ±5%, even more preferably ±1%, and still more preferably±0.1% from the specified value, as such variations are appropriate toperform the disclosed methods.

As used herein, the term “alkene monomer” or “alkene-based substrate”refers to a small molecule or a polymeric molecule comprising at leastone reactive alkenyl group. An “alkenyl group” is an unsaturated, linearor branched or cyclic hydrocarbon group consisting at least onecarbon-carbon double bond. In certain embodiments, the ene-basedsubstrate comprises at least one alkenyl group (C═C).

As used herein, the term “alkyne monomer” or “alkyne-based substrate”refers to a small molecule or a polymeric molecule comprising at leastone reactive alkynyl group. An “alkynyl group” is an unsaturated, linearor branched or cyclic hydrocarbon group consisting at least onecarbon-carbon triple bond. In certain embodiments, the alkyne-basedsubstrate comprises at least one terminal alkynyl group (—C≡CH).

As used herein, the term “ene monomer” refers to a monomer comprising atleast one reactive alkene group, or a reactive alkene equivalent, suchas but not limited to an oxirane group.

As used herein, the term “depolymerization” refers to the reactionwherein a polymer is at least partially converted to at least oneoligomer and/or a monomer, or an oligomer is at least partiallyconverted to at least one smaller oligomer and/or a monomer.

The term “monomer” refers to any discreet chemical compound of anymolecular weight.

As used herein, the term “nucleophilicity value” is defined as thoseobtained from the equation: log k_(20°C.)=_(SN)(N+E), whereinE=electrophilicty parameter, N=nucleophilicty parameter (solventdependent), _(SN)=nucleophile-specific sensitivity parameter (solventdependent). All nucleophilicity values were taken from Baidya, et al.,2007, Angew. Chem. Int. Ed. 46:6176, and are values obtained in MeCN.

As used herein, the term “Type I photoinitiator” refers to a compoundthat undergoes a unimolecular bond cleavage upon irradiation to yieldfree radicals. Non-limiting examples of Type I photoinitiators arebenzoin ethers, benzyl ketals, α-dialkoxy-acetophenones,α-hydroxy-alkylphenones, α-amino-alkylphenones and acyl-phosphineoxides.

As used herein, the term “Type II photoinitiator” refers to acombination of compounds that undergo a bimolecular reaction where theexcited state of the photoinitiator interacts with a second molecule(often known as “co-initiator”) to generate free radicals.

As used herein, the term “pKa” refers to the −log of the aciddissociation constant (Ka) of a compound. All pKa values referred toherein are pKa values for a compound dissolved in water.

As used herein, the term “polymer” refers to a molecule composed ofrepeating structural units typically connected by covalent chemicalbonds. The term “polymer” is also meant to include the terms copolymerand oligomers. In certain embodiments, a polymer comprises a backbone(i.e., the chemical connectivity that defines the central chain of thepolymer, including chemical linkages among the various polymerizedmonomeric units) and a side chain (i.e., the chemical connectivity thatextends away from the backbone).

As used herein, the term “polymerization” or “crosslinking” refers to atleast one reaction that consumes at least one functional group in amonomeric molecule (or monomer), oligomeric molecule (or oligomer) orpolymeric molecule (or polymer), to create at least one chemical linkagebetween at least two distinct molecules (e.g., intermolecular bond), atleast one chemical linkage within the same molecule (e.g.,intramolecular bond), or any combinations thereof. A polymerization orcrosslinking reaction may consume between about 0% and about 100% of theat least one functional group available in the system. In certainembodiments, polymerization or crosslinking of at least one functionalgroup results in about 100% consumption of the at least one functionalgroup. In other embodiments, polymerization or crosslinking of at leastone functional group results in less than about 100% consumption of theat least one functional group.

As used herein, the term “reaction condition” refers to a physicaltreatment, chemical reagent, or combination thereof, which is requiredor optionally required to promote a reaction. Non-limiting examples ofreaction conditions are electromagnetic radiation (such as, but notlimited to visible light), heat, a catalyst, a chemical reagent (suchas, but not limited to, an acid, base, electrophile or nucleophile), anda buffer.

As used herein, the term “reactive” as applied to thiol, isocyanate,oxirane, alkyne or alkene groups indicate that these groups underappropriate conditions may take part in one or more reactions as definedin this application.

As used herein, the term “thiol-ene reaction” refers to an organicreaction between a thiol monomer and an ene/yne monomer. In certainembodiments, the ene monomer is an α,β-unsaturated ester, acid, sulfone,nitrile, ketone, amide, aldehyde, or nitro compound (Hoyle, et al.,Angew. Chem. Intl Ed., 2010, 49(9):1540-1573); the thiol-ene reactioninvolving such reactants is known as “thiol-Michael reaction.”

As used herein, the term “thiol-ene polymerization” refers topolymerization wherein at least one thiol-ene reaction takes place.

As used herein, the term “alkyl”, by itself or as part of anothersubstituent means, unless otherwise stated, a straight or branched chainhydrocarbon having the number of carbon atoms designated (i.e., C₁-C₁₀means one to ten carbon atoms) and includes straight, branched chain, orcyclic substituent groups. Examples include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, andcyclopropylmethyl. Most preferred is (C₁-C₆)alkyl, such as, but notlimited to, ethyl, methyl, isopropyl, isobutyl, n-pentyl, n-hexyl andcyclopropylmethyl.

As used herein, the term “cycloalkyl”, by itself or as part of anothersubstituent means, unless otherwise stated, a cyclic chain hydrocarbonhaving the number of carbon atoms designated (i.e., C₃-C₆ means a cyclicgroup comprising a ring group consisting of three to six carbon atoms)and includes straight, branched chain or cyclic substituent groups.Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, and cyclooctyl. Most preferred is (C₃-C₆)cycloalkyl, suchas, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl.

As used herein, the term “alkenyl”, employed alone or in combinationwith other terms, means, unless otherwise stated, a stablemono-unsaturated or di-unsaturated straight chain or branched chainhydrocarbon group having the stated number of carbon atoms. Examplesinclude vinyl, propenyl (or allyl), crotyl, isopentenyl, butadienyl,1,3-pentadienyl, 1,4-pentadienyl, and the higher homologs and isomers. Afunctional group representing an alkene is exemplified by —CH₂—CH═CH₂.

As used herein, the term “alkynyl”, employed alone or in combinationwith other terms, means, unless otherwise stated, a stable straightchain or branched chain hydrocarbon group with a triple carbon-carbonbond, having the stated number of carbon atoms. Non-limiting examplesinclude ethynyl and propynyl, and the higher homologs and isomers.

As used herein, the term “alkylene” by itself or as part of anothersubstituent means, unless otherwise stated, a straight or branchedhydrocarbon group having the number of carbon atoms designated (i.e.,C₁-C₁₀ means one to ten carbon atoms) and includes straight, branchedchain, or cyclic substituent groups, wherein the group has two openvalencies. Examples include methylene, 1,2-ethylene, 1,1-ethylene,1,1-propylene, 1,2-propylene and 1,3-propylene. Heteroalkylenesubstituents can a group consisting of the stated number of carbon atomsand one or more heteroatoms selected from the group consisting of 0, N,and S, and wherein the nitrogen and sulfur atoms may be optionallyoxidized and the nitrogen heteroatom may be optionally quaternized. Theheteroatom(s) may be placed at any position of the heteroalkyl group,including between the rest of the heteroalkyl group and the fragment towhich it is attached, as well as attached to the most distal carbon atomin the heteroalkyl group.

As used herein, the term “alkenylene”, employed alone or in combinationwith other terms, means, unless otherwise stated, a stablemono-unsaturated or di-unsaturated straight chain or branched chainhydrocarbon group having the stated number of carbon atoms wherein thegroup has two open valencies.

As used herein, the term “alkynylene”, employed alone or in combinationwith other terms, means, unless otherwise stated, a stable straightchain or branched chain hydrocarbon group with a triple carbon-carbonbond, having the stated number of carbon atoms wherein the group has twoopen valencies.

As used herein, the term “substituted alkyl”, “substituted cycloalkyl”,“substituted alkenyl”, “substituted alkynyl”, “substituted alkylene”,“substituted alkenylene” or “substituted alkynylene” means alkyl,cycloalkyl, alkenyl, alkynyl, alkylene, alkenylene, alkynylene asdefined above, substituted by one, two or three substituents selectedfrom the group consisting of C₁-C₁₀ alkyl, halogen, ═O, —OH, alkoxy,tetrahydro-2-H-pyranyl, —NH₂, —N(CH₃)₂, (1-methyl-imidazol-2-yl),pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, —C(═O)OH, trifluoromethyl,—C≡N, —C(═O)O(C₁-C₄)alkyl, —C(═O)NH₂, —C(═O)NH(C₁-C₄)alkyl,—C(═O)N((C₁-C₄)alkyl)₂, —SO₂NH₂, —C(═NH)NH₂, and —NO₂, preferablycontaining one or two substituents selected from halogen, —OH, alkoxy,—NH₂, trifluoromethyl, —N(CH₃)₂, and —C(═O)OH, more preferably selectedfrom halogen, alkoxy and —OH. Examples of substituted alkyls include,but are not limited to, 2,2-difluoropropyl, 2-carboxycyclopentyl and3-chloropropyl.

As used herein, the term “alkoxy” employed alone or in combination withother terms means, unless otherwise stated, an alkyl group having thedesignated number of carbon atoms, as defined above, connected to therest of the molecule via an oxygen atom, such as, for example, methoxy,ethoxy, 1-propoxy, 2-propoxy (isopropoxy) and the higher homologs andisomers. Preferred are (C₁-C₃)alkoxy, such as, but not limited to,ethoxy and methoxy.

As used herein, the term “halo” or “halogen” alone or as part of anothersubstituent means, unless otherwise stated, a fluorine, chlorine,bromine, or iodine atom, preferably, fluorine, chlorine, or bromine,more preferably, fluorine or chlorine.

As used herein, the term “heteroalkyl” by itself or in combination withanother term means, unless otherwise stated, a stable straight orbranched chain alkyl group consisting of the stated number of carbonatoms and one or two heteroatoms selected from the group consisting ofO, N, and S, and wherein the nitrogen and sulfur atoms may be optionallyoxidized and the nitrogen heteroatom may be optionally quaternized. Theheteroatom(s) may be placed at any position of the heteroalkyl group,including between the rest of the heteroalkyl group and the fragment towhich it is attached, as well as attached to the most distal carbon atomin the heteroalkyl group. Examples include: —O—CH₂—CH₂—CH₃,—CH₂—CH₂—CH₂—OH, —CH₂—CH₂—NH—CH₃, —CH₂—S—CH₂—CH₃, and —CH₂CH₂—S(═O)—CH₃.Up to two heteroatoms may be consecutive, such as, for example,—CH₂—NH—OCH₃, or —CH₂—CH₂—S—S—CH₃.

As used herein, the term “heteroalkenyl” by itself or in combinationwith another term means, unless otherwise stated, a stable straight orbranched chain monounsaturated or di-unsaturated hydrocarbon groupconsisting of the stated number of carbon atoms and one or twoheteroatoms selected from the group consisting of O, N, and S, andwherein the nitrogen and sulfur atoms may optionally be oxidized and thenitrogen heteroatom may optionally be quaternized. Up to two heteroatomsmay be placed consecutively. Examples include —CH═CH—O—CH₃,—CH═CH—CH₂—OH, —CH₂—CH═N—OCH₃, —CH═CH—N(CH₃)—CH₃, and —CH₂—CH═CH—CH₂—SH.

As used herein, the term “aromatic” refers to a carbocycle orheterocycle with one or more polyunsaturated rings and having aromaticcharacter, i.e. having (4n+2) delocalized π(pi) electrons, where n is aninteger.

As used herein, the term “aryl”, employed alone or in combination withother terms, means, unless otherwise stated, a carbocyclic aromaticsystem containing one or more rings (typically one, two or three rings)wherein such rings may be attached together in a pendent manner, such asa biphenyl, or may be fused, such as naphthalene. Examples includephenyl, anthracyl, and naphthyl. Preferred are phenyl and naphthyl, mostpreferred is phenyl.

As used herein, the term “heterocycle” or “heterocyclyl” or“heterocyclic” by itself or as part of another substituent means, unlessotherwise stated, an unsubstituted or substituted, stable, mono- ormulti-cyclic heterocyclic ring system that consists of carbon atoms andat least one heteroatom selected from the group consisting of N, O, andS, and wherein the nitrogen and sulfur heteroatoms may be optionallyoxidized, and the nitrogen atom may be optionally quaternized. Theheterocyclic system may be attached, unless otherwise stated, at anyheteroatom or carbon atom that affords a stable structure. A heterocyclemay be aromatic or non-aromatic in nature. In one embodiment, theheterocycle is a heteroaryl.

As used herein, the term “heteroaryl” or “heteroaromatic” refers to aheterocycle having aromatic character. A polycyclic heteroaryl mayinclude one or more rings that are partially saturated. Examples includetetrahydroquinoline and 2,3-dihydrobenzofuryl.

Examples of non-aromatic heterocycles include monocyclic groups such asaziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine,pyrroline, imidazoline, pyrazolidine, dioxolane, sulfolane,2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, thiophane,piperidine, 1,2,3,6-tetrahydropyridine, 1,4-dihydropyridine, piperazine,morpholine, thiomorpholine, pyran, 2,3-dihydropyran, tetrahydropyran,1,4-dioxane, 1,3-dioxane, homopiperazine, homopiperidine, 1,3-dioxepane,4,7-dihydro-1,3-dioxepin and hexamethyleneoxide.

Examples of heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl(such as, but not limited to, 2- and 4-pyrimidinyl), pyridazinyl,thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl,isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl,tetrazolyl, 1,2,3-thiadiazolyl, 1,2,3-oxadiazolyl, 1,3,4-thiadiazolyland 1,3,4-oxadiazolyl.

Examples of polycyclic heterocycles include indolyl (such as, but notlimited to, 3-, 4-, 5-, 6- and 7-indolyl), indolinyl, quinolyl,tetrahydroquinolyl, isoquinolyl (such as, but not limited to, 1- and5-isoquinolyl), 1,2,3,4-tetrahydroisoquinolyl, cinnolinyl, quinoxalinyl(such as, but not limited to, 2- and 5-quinoxalinyl), quinazolinyl,phthalazinyl, 1,8-naphthyridinyl, 1,4-benzodioxanyl, coumarin,dihydrocoumarin, 1,5-naphthyridinyl, benzofuryl (such as, but notlimited to, 3-, 4-, 5-, 6- and 7-benzofuryl), 2,3-dihydrobenzofuryl,1,2-benzisoxazolyl, benzothienyl (such as, but not limited to, 3-, 4-,5-, 6-, and 7-benzothienyl), benzoxazolyl, benzothiazolyl (such as, butnot limited to, 2-benzothiazolyl and 5-benzothiazolyl), purinyl,benzimidazolyl, benztriazolyl, thioxanthinyl, carbazolyl, carbolinyl,acridinyl, pyrrolizidinyl, and quinolizidinyl.

The aforementioned listing of heterocyclyl and heteroaryl moieties isintended to be representative and not limiting.

As used herein, the term “substituted” means that an atom or group ofatoms has replaced hydrogen as the substituent attached to anothergroup.

For aryl, aryl-(C₁-C₃)alkyl and heterocyclyl groups, the term“substituted” as applied to the rings of these groups refers to anylevel of substitution, namely mono-, di-, tri-, tetra-, orpenta-substitution, where such substitution is permitted. Thesubstituents are independently selected, and substitution may be at anychemically accessible position. In one embodiment, the substituents varyin number between one and four. In another embodiment, the substituentsvary in number between one and three. In yet another embodiment, thesubstituents vary in number between one and two. In yet anotherembodiment, the substituents are independently selected from the groupconsisting of C₁₋₆ alkyl, —OH, C₁₋₆ alkoxy, halo, amino, acetamido andnitro. As used herein, where a substituent is an alkyl or alkoxy group,the carbon chain may be branched, straight or cyclic, with straightbeing preferred.

“Instructional material” as that term is used herein includes apublication, a recording, a diagram, or any other medium of expressionthat can be used to communicate the usefulness of the composition and/orcompound of the invention in a kit. The instructional material of thekit may, for example, be affixed to a container that contains thecompound and/or composition of the invention or be shipped together witha container that contains the compound and/or composition.

Throughout this disclosure, various aspects of the invention may bepresented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges as well asindividual numerical values within that range and, when appropriate,partial integers of the numerical values within ranges. For example,description of a range such as from 1 to 6 should be considered to havespecifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well asindividual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5,5.3, and 6. This applies regardless of the breadth of the range.

The following abbreviations are used herein: CAN(s)=covalent adaptablenetwork(s); DAEC=diallyloctanedionate;DBU=1,8-Diazabicyclo[5,4,0]undec-7-ene; Di-PETMP=Dipentaerythritolhexa(3-mercaptopropionate); DMAP=4-Dimethylaminopyridine; DMPA=Irgacure651 (2,2-Dimethoxy-2-phenylacetophonone); DSDAE=disulfide di-allylether;ETTMP=Ethoxilated-Trimethylolpropan Tri(3-Mercaptopropionate);FT-IR=Fourier transform infrared spectroscopy;HABI-1=2-chloro-4-(octyloxy)benzaldehyde;HABI-2=2-(2-chloro-4-(octyloxy)phenyl)-1-methyl-4,5-diphenyl-1H-imidazole;HABI-Cl=2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-2′H-1,2′-biimidazole;HABI-O-n-oct=2,2′-bis(2-chloro-4-(octyloxy)phenyl)-4,4′,5,5′-tetraphenyl-2′H-1,2′-biimidazole;IR=infrared; MPa, megapascal; NMR=nuclear magnetic resonancespectroscopy; PA=photoacid (in certain embodiments,2-(2-nitrophenyl)propyl 2-phenylacetate); PB=photobase (in certainembodiments:

PCL4MP=polycaprolactone tetra(3-mercaptopropionate);PETMP=Pentaerythritol tetrakis(3-mercaptopropionate);PMDETA=N,N,N′,N″,N″-pentamethyldiethylenetriamine; RAFT=reversibleaddition-fragmentation chain transfer;TE-1=3-((4-(allyloxy)-4-oxobutanoyl)thio)propanoic acid;TEA=Triethylamine; TEDAE=thioester di-allyl ether (allyl4-((3-(allyloxy)-3-oxopropyl)thio)-4-oxobutanoate); TEDI=thioesterdi-isocyanate; TEMPIC=Tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate; TMPTMP=trimethylolpropanetris(3-mercaptopropionate); UV=ultraviolet.

Compounds and Compositions

In certain embodiments, the invention includes a composition comprisingat least one of the following:

-   -   (a) at least one multifunctional thioester containing monomer of        Formula (I):

wherein in (I):

A¹ and A² are each independently selected from the group consisting ofoptionally substituted C₁-C₁₅ alkylene, optionally substituted C₂-C₁₅alkenylene, optionally substituted C₂-C₁₅ alkynylene, optionallysubstituted C₁₂-C₁₅ heteroalkylene, optionally substituted C₂-C₁₅heteroalkenylene and optionally substituted C₂-C₁₅ heteroalkynylene;

E¹ and E² are each independently selected from the group consisting of:

-   -   wherein each instance of Y¹ is independently selected from the        group consisting of 0 and NR¹; and each instance of R¹ is        independently selected from the group consisting of H and C₁-C₆        alkyl;

m1 is 0 or 1; m2 is 0 or 1;

X¹ is

wherein: bond a is to A¹, bond b is to E¹, Q is CH₂ or

and n is 0, 1, 2, 3, 4, 5 or 6;

X² is

wherein: bond a is to A², bond b is to E², Q is CH₂ or

and n is 0, 1, 2, 3, 4, 5 or 6;

each instance of Y², and Y³ is independently selected from the groupconsisting of CR¹ ₂, O and NR¹; and

each instance of R¹ is independently selected from the group consistingof H and C₁-C₆ alkyl;

-   -   (b) at least one multifunctional thiol monomer; and    -   (c) at least one selected from the group consisting of a base        and a nucleophile.

In certain embodiments, the multifunctional thioester containing monomerof Formula (I) is a monomer of Formula (Ia):

wherein A¹, A², E¹ and E² are defined as elsewhere herein.

In other embodiments, the multifunctional thioester containing monomeris selected from the group consisting of:

wherein m is 0, 1, 2, 3, 4, 5 or 6.

The multifunctional thiol monomer can be any monomer commonly employedin the art that comprises two or more thiol (—SH) terminalfunctionalities.

In certain embodiments, the multifunctional thiol monomer is selectedfrom the group consisting of:

wherein each instance of n is an integer from 0 to 500.

In other embodiments, the multifunctional thiol monomer is selected fromthe group consisting of pentaerythritol tetramercaptopropionate (PETMP);ethylene glycol bis(3-mercaptopropionate) (EGBMP); trimethylolpropanetris(3-mercaptopropionate)(TMPMP); 2,4,6-trioxo-1,3,5-triazina-triy(triethyl-tris (3-mercapto propionate); 1,2-ethanedithiol;1,3-propanedithiol; 1,4-butanedithiol; 1,5-pentanedithiol;1,6-hexanedithiol; 1,8-octanedithiol; 1,9-nonanedithiol;1,11-undecanedithiol; 1,16-hexadecanedithiol;2,5-dimercaptomethyl-1,4-dithiane; pentaerythritol tetramercaptoacetate;trimethylolpropane trimercaptoacetate; glycol dimercaptoacetate;2,3-dimercapto-1-propanol; DL-dithiothreitol; 2-mercaptoethylsulfide;2,3-(dimercaptoethylthio)-1-mercaptopropane; 1,2,3-trimercaptopropane;toluenedithiol; benzenedithiol; biphenyldithiol; benzenedimethanethiol;xylylenedithiol; 4,4′-dimercaptostilbene and glycoldimercaptopropionate.

In certain embodiments, the base is selected such that pKa (base'sconjugate acid) is equal to or greater than about [pKa (most acidicthiol group on the thiol monomer)−1 pKa unit]. In other embodiments, thenucleophile has a nucleophilicity value (N) greater than about 10. Inyet other embodiments, the base has a conjugate acid with a pKa rangingfrom about 2 to about 15. In yet other embodiments, the base is acompound capable of deprotonating at least about 10% of the free thiolgroups in the composition.

In certain embodiments, the base is selected from the group consistingof tetramethylguanidine (TMG), 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU),N,N-Diisopropylethylamine (DIPEA or Hunig's base), 4-tert-butylpyridine, triethylamine (TEA), andN,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA).

In certain embodiments, the base is a thiolate containing compound. Inother embodiments, the base is a thiolate salt. In yet otherembodiments, the base is an alkylthiolate salt or an arylthiolate salt.

In certain embodiments, the nucleophile is selected from the groupconsisting of quinuclidine, 1,4-diazabicyclo[2.2.2]octane (DABCO),4-Dimethylaminopyridine (DMAP), PPh₃ P(nBu)₃, P(tBu)₃, PCy₃, and PMe₃.In other embodiments, the nucleophile is an N-heterocyclic carbene. Inyet other embodiments, the nucleophile is an N-heterocyclic carbeneselected from the group consisting of:

In certain embodiments, the composition comprises at least onepH-altering compound that alters the pH of the composition uponphoto-excitation or thermal-excitation. In certain embodiments, thepH-altering compound is a photo-activatable or thermal-activatable acid,or photoactivatable or thermal-activatable base.

In certain embodiments, the composition comprises a photo-activatablebase. In other embodiments, the photo-activatable base does notdeprotonate at least about 10% of the free thiol groups in thecomposition in its inactive state (without photo-activation), and iscapable of deprotonating at least about 10% of the free thiol groups inthe composition after photo-activation.

In certain embodiments, the photo-activatable base is a basic moleculecoupled to a photocleavable protecting group. In other embodiments, thephoto-activatable base is activated upon exposure to light in the IR(700-1,000,000 nm), visible (400-700 nm) or UV (10-400 nm) ranges. Inyet other embodiments, the photo-activatable base is activated uponexposure to light with a wavelength shorter than about 450 nm. In yetother embodiments, the photo-activatable base is any photo-activatablebase known in the art, such as but not limited to those described in:Chem. Rev., 2013, 113, 119-191; ACS Macro Lett., 2016, 5, 229-233;Macromolecules, 2014, 47, 6159-6165; and ACS Macro Lett, 2014, 3,315-318, which are incorporated by reference in their entireties herein.In yet other embodiments, the photo-activatable base is a compound of ageneral formula selected from the group consisting of:

In yet other embodiments, the photo-activatable base is a compoundselected from the group consisting of:

1,2-Diisopropyl-3-[Bis(dimethylamino)methylene]guanidium2-(3-benzoylphenyl)propionate,1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate,and (Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminiumtetrakis(3-fluorophenyl) borate.

In certain embodiments, the composition comprises a thermal-activatablebase. In certain embodiments, the thermal-activatable base does notdeprotonate at least about 10% of the free thiol groups in thecomposition in an inactive state (without thermal activation), anddeprotonates at least about 10% of the free thiol groups in thecomposition after thermal activation.

In certain embodiments, the thermal-activatable base is a basic moleculecoupled to a thermally cleavable protecting group. In other embodiments,the thermal-activatable base is activated upon exposure to temperaturesof about 30° C. to about 200° C. In yet other embodiments, thethermal-activatable base is any thermally activated base known in theart, such as but not limited to those described in Angew. Chem. Int. Ed.2005, 44, 4964-4968; Macromol. Rapid Commun., 2014, 35, 682-701; Catal.Sci. Technol, 2014, 4, 2466-2479; and J. Org. Chem., 2005, 70,5335-5338, which are incorporated by reference in their entirety. Incertain embodiments, the thermal-activatable base is a compound of ageneral formula selected from the group consisting of:

In yet other embodiments, the thermal-activatable base is a compoundselected from the group consisting of:

In certain embodiments, the composition further comprises aphoto-activatable acid. In other embodiments, the photo-activatable acidhas a pKa value greater than the pKa of the least acidic thiol group onthe thiol monomer in an inactive state (without photo-activation), butundergoes a chemical and/or structural change or rearrangement uponexposure to light, thereby generating a compound that has a pKa valueless than the pKa of the least acidic thiol on the thiol monomer. In yetother embodiments, the acid generated is of sufficient strength toneutralize the one or more bases and/or nucleophiles present in thecomposition. In yet other embodiments, the pH-altering compound is acompound comprising an acidic molecule coupled to a photocleavableprotecting group. In yet other embodiments, the photo-activatable acidis activated upon exposure to light in the IR (700-1,000,000 nm),visible (400-700 nm) or UV (10-400 nm) ranges. In yet other embodiments,the photo-activatable acid is activated upon exposure to light with awavelength shorter than about 450 nm. In yet other embodiments, thephoto-activatable acid is any light activated acid known in the art,such as but not limited to those described in Hinsberg and Wallraff,Lithographic Resists, Kirk-Othmer Encyclopedia of Chemical Technology,Wiley-VCH, Weinheim, 2005, which is incorporated by reference in itsentirety. In yet other embodiments, the photo-activatable acid is acompound selected from the group consisting of:

Bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate,Bis(4-tert-butylphenyl)iodonium p-toluenesulfonate,Bis(4-tert-butylphenyl)iodonium, Boc-methoxyphenyldiphenylsulfoniumtriflate, (4-tert-Butylphenyl)diphenylsulfonium triflate,Diphenyliodonium hexafluorophosphate, Diphenyliodonium nitrate,Diphenyliodonium perfluoro-1-butanesulfonate, Diphenyliodoniump-toluenesulfonate, Diphenyliodonium triflate,(4-Fluorophenyl)diphenylsulfonium triflate, N-Hydroxynaphthalimidetriflate, N-Hydroxy-5-norbornene-2,3-dicarboximideperfluoro-1-butanesulfonate, (4-Iodophenyl)diphenylsulfonium triflate,(4-Methoxyphenyl) diphenylsulfonium triflate,2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,(4-Methylphenyl)diphenylsulfonium triflate, (4-Methylthiophenyl)methylphenyl sulfonium triflate, (4-Phenoxyphenyl)diphenylsulfonium triflate,(4-Phenylthiophenyl)diphenylsulfonium triflate, Triarylsulfoniumhexafluorophosphate salts, Triphenylsulfoniumperfluoro-1-butanesufonate, Triphenylsulfonium triflate,Tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate, andTris(4-tert-butylphenyl)sulfonium triflate.

In certain embodiments, the composition further comprises athermal-activatable acid. In other embodiments, the thermal-activatableacid has a pKa value greater than the pKa of the least acidic thiolgroup on the thiol monomer in an inactive state (without thermalactivation) but undergoes a chemical and/or structural change orrearrangement upon exposure to heat, thereby generating a compound whichhas a pKa value less than the pKa of the least acidic thiol on the thiolmonomer. In yet other embodiments, the acid generated by thermalactivation is of sufficient strength to neutralize the one or more basesand/or nucleophiles present in the composition. In yet otherembodiments, the pH-altering compound is an acidic molecule coupled to athermally cleavable protecting group. In yet other embodiments, thethermal-activatable acid is activated upon exposure to temperatures ofabout 30° C. to about 200° C. In yet other embodiments, thethermal-activatable acid is any thermally activated acid known in theart, such as but not limited to those described in Proc. SPIE 399,Advances in Resist Technology and Processing XVII, (23 Jun. 200), whichis incorporated by reference in its entirety. In certain embodiments,the thermal-activatable acid is one or more compounds selected from thegroup consisting of:

In certain embodiments, the composition further comprises one or morepolymerization initiators. In other embodiments, the compositioncomprises one or more polymerization initiators selected from the groupconsisting of photoinitiators, thermal initiators and redox initiators.

In certain embodiments, the photoinitiator is reactive upon exposure tolight in the IR (700-1,000,000 nm), visible (400-700 nm) or UV (10-400nm). In other embodiments, the photoinitiator is activated upon exposureto a different light wavelength than the light wavelength used toactivate any photo-excitation triggered pH-altering compound(s) presentin the composition, thereby allowing for independent activation of thepH altering compound and the photoinitiator. In other embodiments, thephotoinitiator is selected from the group consisting of Type-1 andType-2 photoinitiators. In yet other embodiments, the photoinitiator isa compound belonging to a class selected from the group consisting ofacyl phosphines, ketones, diimidazoles, acyl germaniums, thioketones,dithiocarbonates, trithiocarbonates, camphorquinones and camphoramines.In yet other embodiments, the photoinitiator is selected from the groupconsisting of: acetophenone, benzophenone, 2-phenylacetophenone,2,2-dimethoxy-2-phenylacetophenone,Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone,2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one,Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Ethyl(2,4,6-trimethylbenzoyl) phenyl phosphinate, lithiumphenyl-2,4,6-trimethylbenzoylphosphinate,

In certain embodiments, the thermal initiator is reactive upon exposureto temperatures of about 30° C. to about 200° C. In other embodiments,the thermal initiator is a compound selected from the group consistingof tert-Amyl peroxybenzoate, 4,4-Azobis(4-cyanovaleric acid),1,1′-Azobis(cyclohexanecarbonitrile), 2,2′-Azobisisobutyronitrile(AIBN), Benzoyl peroxide, 2,2-Bis(tert-butylperoxy)butane,1,1-Bis(tert-butylperoxy)cyclohexane,2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane,2,5-Bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,Bis(1-(tert-butylperoxy)-1-methylethyl)benzene,1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-Butylhydroperoxide, tert-Butyl peracetate, tert-Butyl peroxide, tert-Butylperoxybenzoate, tert-Butylperoxy isopropyl carbonate, cumenehydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroylperoxide, 2,4-pentanedione peroxide, peracetic acid and potassiumpersulfate.

In certain embodiments, the redox initiator is one or more compoundsselected from the group consisting of: sodium iodide/hydrogen peroxide,potassium iodide/hydrogen peroxide, benzoyl peroxide/dimethyaniline,benzoyl peroxide/N,N-dimethyl p-toluidine, benzoylperoxide/4-N,N-dimethylaminophenethyl alcohol, benzoyl peroxide/ethyl4-dimethylaminobenzoate, glucose oxidase/oxygen/iron(II) sulfate andcopper(II) sulfate/sodium ascorbate.

In certain embodiments, the composition comprises the at least onemultifunctional thioester containing monomer and at least onemultifunctional thiol monomer in a relative ratio such that the totalnumber of thiol functionalities present on the at least onemultifunctional thiol monomer within the composition is greater than thetotal number of E¹ and E² functionalities present on the at least onemultifunctional thioester containing monomer. In certain non-limitingembodiments, the composition comprises more than 2 equivalents oftrifunctional thiol monomer per 3 equivalents of difunctional thioestermonomer; in other embodiments, the composition comprises more than 1equivalent of tetrafunctional thiol monomer per 2 equivalents ofdifunctional thioester monomer.

Covalent Adaptable Network Polymers

In certain embodiments, the invention includes a composition comprisinga cross-linked, CAN polymer comprising a plurality of thioester linkagesand a plurality of free thiol (—SH) groups, and at least one exchangecatalyst selected from a base and a nucleophile; wherein the base is acompound capable of deprotonating at least about 10% of the free thiolgroups in the composition; and wherein the nucleophile has anucleophilicity value (N) greater than about 10.

In certain embodiments, the at least one exchange catalyst is covalentlybound to the CAN polymer. In other embodiments, the at least oneexchange catalyst is not covalently bound to the CAN polymer.

In certain embodiments, the cross-linked CAN is formed through one ormore processes selected from the group consisting of thiol-enepolymerization, thiol-alkyne polymerization, thiol-acrylatepolymerization, thiol-methacrylate, acrylate polymerization,methacrylate polymerization, styrene polymerization, alcohol-isocyanatepolymerization, thiol-isocyanate polymerization, thiol-epoxidepolymerization, thiol-isothiocyanate polymerization, thiol-halidepolymerization, thiol-malemide, thiol-activated ester polymerization,copper-catalyzed azide alkyne polymerization, strain-promoted azidealkyne polymerization, and epoxide-carboxylic acid polymerization.

In certain embodiments, the at least one exchange catalyst is a base,nucleophile, photo-activatable base, and/or thermal-activatable base asdescribed elsewhere herein.

In certain embodiments, the cross-linked CAN further comprises at leastone pH-altering compound selected from a photo-activatable acid and athermal-activatable acid. In other embodiments, the photo-activatableacid and the thermal-activatable acid are compounds as describedelsewhere herein.

In certain embodiments, a composition of the invention describedelsewhere herein, comprising at least one multifunctional thioestercontaining monomer, at least one multifunctional thiol monomer and atleast one of a base and a nucleophile, is capable of forming across-linked CAN polymer. The invention also provides a CAN polymerformed from a composition of the invention, but is not limited to onlyCAN polymers formed from the compositions described elsewhere herein. Incertain embodiments, the CAN is formed through activation of at leastone selected from the group consisting of a photoinitiator, thermalinitiator and redox initiator, which initiates radical based thiol-enepolymerization between the at least one multifunctional thioestercontaining monomer and the at least one multifunctional thiol monomer.

In certain embodiments, the cross-linked CAN of the invention undergoesbond exchange. Without being limited to any single theory, the bondexchange occurs through nucleophilic attack on a thioester functionalityby an unbound thiol group. This nucleophilic attack is catalyzed by thebases/nucleophiles in the composition.

In certain embodiments, the bond exchange imparts plasticity to the CANsof the invention. In certain embodiments, the CANs of the invention canbe remolded and reformed after initial polymerization. The ability toundergo bond exchange allows for the compositions of the invention torespond to applied pressure and undergo stress relaxation. In certainembodiments, the bond exchange alleviates polymerization induced stress.In certain embodiments, the CANs compositions of the invention canself-repair through bond exchange.

In certain embodiments, the bond exchange is selectively activated ordeactivated through exposure to light in the IR (700-1,000,000 nm),visible (400-700 nm) or UV (10-400 nm) ranges. In other embodiments, thebond exchange is activated or deactivated through exposure to lightbelow 450 nm. In other embodiments, this photoswitching property occursat ambient temperatures (about 18° C. to about 30° C.). In yet otherembodiments, the photoswitching property occurs without applying heat.

In certain embodiments, the bond exchange is selectively activated ordeactivated through exposure to heat. In other embodiments, the bondexchange is activated by exposure to temperatures of about 30° C. toabout 200° C.

In certain embodiments, the bond exchange properties of the CANs arelocally activated or deactivated through the use of localizedirradiation with a light source, thereby allowing for spatial and/ortemporal control of the rapid bond exchange properties. In otherembodiments, the bond exchange properties of the CANs are locallyactivated or deactivated through the use of localized heating of thenetwork, thereby allowing for spatial and temporal control of the rapidbond exchange properties.

In certain embodiments, the CAN (or a composition comprising the CAN)comprises a photo-activatable base or thermal-activatable base, whereinthe CAN does not exhibit significant bond exchange before activation ofthe base (behaving like a thermoset) but does exhibit bond exchangeafter activation of the base. In other embodiments, activation of thebase converts the CAN polymer from an elastic polymer to a plasticpolymer.

In certain embodiments, the CAN (or a composition comprising the CAN)comprises a base and/or nucleophile and a photo-activatable acid orthermal-activatable acid, wherein the CAN polymer exhibits bond exchangebefore activation of the acid but does not exhibit significant bondexchange after activation of the acid. In other embodiments, activationof the acid converts the CAN polymer from a plastic polymer to anelastic polymer. Without being limited to any single theory, theactivation of the acid neutralizes and/or deactivates the base and/ornucleophile, preventing deprotonation of the free thiol groups, therebyhindering or preventing catalysis of the rapid bond exchange.

In certain embodiments, the CAN polymers can be shaped or molded intosubstantially any shape desired for a given application. In otherembodiments, the CAN polymers can be reshaped after molding. In yetother embodiments, the CAN polymers can be molded, and behave like athermoset (cannot be reshaped), until a photo-activatable orthermal-activatable base is activated, thereby allowing for the CANpolymer to be reshaped. In yet other embodiments, the CAN polymers canbe molded and reshaped/remolded until activation of a photo-activatableor thermal-activatable acid is activated, thereby setting the CANpolymer and preventing any further reshaping.

In certain embodiments, the CAN polymers can self-repair when damaged.In other embodiments, the CAN polymers can be separated into distinctpieces and reformed. In other embodiments, the CAN polymers can bereshaped to repair fractures, cracks and ruptures.

In other embodiments, the compositions of the invention are suitable foruse in optical applications, for example as lenses. In yet otherembodiments, the compositions of the invention are suitable for use asadhesives or bonding agents. In yet other embodiments, the compositionsof the invention are suitable for use in 3D printing applications. Inyet other embodiments, the compositions of the invention are suitablefor use as hard coatings. Uses for the CANs of the invention are notlimited to these examples and additional uses would be apparent to thoseskilled in the art.

In certain embodiments, the CANs of the invention are transparent. Inother embodiments, the compositions are colorless. In yet otherembodiments, the compositions further comprise one or more coloringagents or dyes.

In certain embodiments, the invention provides a solid material particleembedded in a CAN matrix. In other embodiments, the solid materialparticle is a silica particle. In other embodiments, the compositioncomprises silica particles embedded in a CAN matrix. In yet otherembodiments, the silica particles can have an average diameter of about0.1 μm to about 100 μm.

In certain embodiments, the CANs of the invention are insoluble inaqueous and/or organic solutions. In other embodiments, the CANs of theinvention can be controllably degraded through the addition of one ormore additives.

In certain embodiments, the CANs of the invention are degraded tosoluble oligomers through addition of excess multifunctional thiolmonomers and a suitable organic solvent capable of solvating theoligomers, in the presence of an active base and/or nucleophile asdescribed elsewhere herein. Without being limited to any particulartheory, in the presence of an excess of thiol monomer, the CAN polymersundergo bond exchange and form oligomers due to a deficit of “ene”monomers for the thiol monomers to react with. In certain embodiments,the oligomers can be solubilized in solvents such as, but not limitedto, aqueous solutions, organic ketone solvents, organic ester solvents,chlorinated hydrocarbon solvents, aliphatic hydrocarbon solvents,aromatic solvents, organic alcohols, organic ether solvents, organicacetamide solvents, and sulfoxide/sulfone solvents. In otherembodiments, the oligomers can be solubilized in one or more solventsselected from the group consisting of acetone, ethyl acetate,dichloromethane, chloroform, carbon tetrachloride, hexanes, toluene,benzene, xylenes, water, methanol, ethanol, isopropanol, 2-methyltetrahydrofuran, tetrahydrofuran, diethyl ether, dimethylformamide,dimethylacetamide, dimethylsulfoxide and any combinations thereof. Incertain embodiments, the oligomers have a molecular weight of about 0.5to about 20 kDa. In certain embodiments, the CAN polymer composition isdegraded through the addition of about 1 to about 100 equivalents ofexcess multifunctional thiol monomer. In other embodiments, the CANpolymer composition is degraded through the addition of about 5 to about10 equivalents of excess multifunctional thiol monomer.

In certain embodiments, the soluble oligomers can be reformed into CANpolymer compositions through the addition of multifunctional thioestercontaining monomers followed. In certain embodiments, adding an amountof multifunctional thioester containing monomer restores the ratio ofmultifunctional thioester containing monomer to multifunctional thiolmonomer in the original CAN polymer composition. In other embodiments,the reformed CAN polymers have identical physical properties to theoriginal CAN polymers.

Kits

The invention includes a kit comprising a composition of the inventioncomprising at least one, or all of the following: (a) at least onemultifunctional thioester containing monomer of Formula (I) or (Ia); (b)at least one multifunctional thiol monomer; (c) at least one selectedfrom the group consisting of a base and a nucleophile; and aninstructional material for use thereof.

In certain embodiments, the at least one base and nucleophile are basesand nucleophiles as described elsewhere herein. In certain embodiments,the base is a photo-activatable base or thermal-activatable base, asdescribed elsewhere herein. In other embodiments, the kit furthercomprises a photo-activatable acid or thermal-activatable acid, asdescribed elsewhere herein. In certain embodiments, the kit furthercomprises at least one selected from the group consisting of aphotoinitiator, a thermal initiator and a redox initiator. In yet otherembodiments, the kit further comprises a light source capable ofproducing light sufficient to activate at least one of thephotoinitiator, the photo-activatable base and the photo-activatableacid. In other embodiments, the kit further comprises a heat sourcecapable of producing heat sufficient to activate at least one of thethermal initiator, the thermal-activatable base and thethermal-activatable acid. The instructional material included in the kitcomprises instructions for forming the CAN polymers of the invention,molding the CAN polymers of the invention, recycling the CAN polymers ofthe invention and selectively activating or deactivating thephotoswitchable properties of the CAN polymers of the invention.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures, embodiments, claims, and examples described herein.Such equivalents were considered to be within the scope of thisinvention and covered by the claims appended hereto. For example, itshould be understood, that modifications in reaction conditions,including but not limited to reaction times, reaction size/volume, andexperimental reagents, such as solvents, catalysts, pressures,atmospheric conditions, e.g., nitrogen atmosphere, andreducing/oxidizing agents, with art-recognized alternatives and using nomore than routine experimentation, are within the scope of the presentapplication.

It is to be understood that wherever values and ranges are providedherein, all values and ranges encompassed by these values and ranges,are meant to be encompassed within the scope of the present invention.Moreover, all values that fall within these ranges, as well as the upperor lower limits of a range of values, are also contemplated by thepresent application.

The following examples further illustrate aspects of the presentinvention. However, they are in no way a limitation of the teachings ordisclosure of the present invention as set forth herein.

EXAMPLES

The invention is now described with reference to the following Examples.These Examples are provided for the purpose of illustration only, andthe invention is not limited to these Examples, but rather encompassesall variations that are evident as a result of the teachings providedherein.

Materials

Unless described otherwise, the materials used in the experiments wereobtained from commercial sources or obtained by methods known in theart, and used without further purification.

Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), tri(ethyleneglycol) di(vinyl ether) (DVE-3), triethylamine (TEA),N,N,N′,N″-pentamethyldiethylenetriamine (PMDETA),1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 4-dimethylaminopyridine(DMAP), toluenesulfonic acid monohydrate (TsOH), allyl alcohol,trimethylolpropane tris(3-mercaptopropionate) (TMPTMP),methylhydroquinone and 3,3′-dithiodipropionic acid were purchased fromSigma-Aldrich. Dipentaerythritol hexa(3-mercaptopropionate) (Di-PETMP),ethoxylated-trimethylolpropan tri(3-Mercaptopropionate) (ETTMP 700 andETTMP 1300), polycaprolactone tetra(3-mercaptopropionate) (PCL4MP) weredonated from Bruno Bock. Irgacure 184, Irgacure 651 (DMPA) and Irgacure907 were purchased from Ciba. Succinic anhydride and anhydrous sodiumsulfate were purchased from Acros Organics and used as received.Irgacure 651 (DMPA) and Irgacure 819 were donated by BASF. Diallyladipate was purchased from TCI. All reactants and solvents were used asreceived.

Polymer Film Preparation

Resins were prepared by combining the tetrathiol (PETMP), TEDAE,photoinitiator (DMPA), and a base catalyst (TEA, PMDETA, or DBU) in aglass vial and vortexing to dissolve the initiator. Unless otherwisenoted, typical formulations incorporated a 2:1 ratio of thiol:enefunctional groups, and between 0.02 and 0.08 equivalents of base perthiol group. Once the photoinitiator had completely dissolved, the resinwas placed between glass slides treated with Rain-X (ITW Global Brands,Houston, Tex.) using 250 μm thick spacers (Small Parts Inc., Logansport,Ind.). The film was then cured with 365 nm light at approximately 5mW/cm² for 5 minutes.

For the creep experiments shown in FIG. 5 , the following formulationswere used. The experimental formulation included PETMP, TEDAE, a 2:1thiol:ene ratio, 0.05 eq PMDETA per thiol, and 0.01 eq DMPA per thiol.The control formulations were prepared similarly, but with the followingadjustments. The “no thiol” condition included a 2:1 ene:thiol ratio, toensure no thiol groups remained after polymerization, and to achieve apolymer with similar crosslinking density to the experimental condition.For the “no base” condition, no PMDETA was added. For the “no thioester”condition, tri(ethylene glycol) di(vinyl ether) (DVE-3) was used inplace of TEDAE.

Stress Relaxation and Creep Experiments

All stress relaxation and creep experiments were performed in tensileelongation using a Q800 DMA (TA Instruments) or a RSA-G2 (TAInstruments). For stress relaxation, the built-in stress relaxation modewas used, with either a 10% or 20% strain for ambient temperature tests.For temperature stepping tests, which are performed repeatedly on thesame sample, a 4% strain was used to avoid significant sampledeformation between scans. Films were cut into rectangular sections andmeasured with calipers prior to loading into the DMA.

Dynamic Mechanical Analysis of the Glass Transition Temperature

The glass transition temperature was determined on a Q800 DMA (TAInstruments) using a ramp rate of 3° C./min and a frequency of 3 Hz,with a fixed oscillatory strain of 0.025%. Films were cut intorectangular sections and measured with calipers prior to loading intothe DMA.

Pristine Photopolymer Preparation

The UV-curable thioester containing thiol-ene resins were prepared bydissolving DMPA or Irgacure 184 (1 mol % with respect to alkene groups)in a combination of thiol and allyl ether monomers. The resin was castedbetween glass slides with 250 μm thick spacers and subsequentlyirradiated by a BlackRay lamp (8 mW/cm² @365 nm) for 5 mins.

The UV-curable thiol-isocyanate resins were prepared by dissolvingIrgacure 907 (0.55 wt % with respect to total monomers) in a combinationof stoichiometric PETMP and thioester diisocyanate. The mixture washomogenized by a speedmixer for 90 sec (FlackTek Inc, model DAC 150.1FV-K) and immediately casted and irradiated by a BlackRay lamp for 10mins, subsequently being post-cured at 80° C. overnight.

The UV-curable disulfide containing thiol-ene resins were prepared bydissolving Irgacure 184 (1 mol % with respect to total monomers) in acombination of stoichiometric PETMP and DSDAE. The mixture was castedbetween glass slides and irradiated by a BlackRay lamp for 20 mins,subsequently being post-cured at 80° C. overnight.

Recycling Procedure

Polythioesters were recycled by degrading via thiol-excessthiol-thioester exchange reactions. Polymer samples were cut into ˜20cm² pieces, then mixed with a certain multiple equivalency of thiolmonomers, an equal mass of reagent grade acetone and 20 wt % of TEA (50mol % to thioestser groups) was added (both with respect to the totalnonvolatile compounds). The mixture was stirred at ambient temperaturewithout precautions to guard the reaction from atmospheric oxygen ormoisture. Generally, the thiol-ene polymers completely disappearedwithin 3 hours. The oligomers were purified by removing the volatiles,particularly, by rotary evaporation followed by high vacuum at 85° C.until the formation of bubbles had ceased.

Repolymerizing Procedure

The reclaimed thioester containing thiol-ene resins were prepared bymixing devolatilized recycling oligomers with stoichiometric thioesterdiallyl ether monomers (with pre-dissolved 1 mol % DMPA). The mixturewas polymerized under the same condition as the pristine samples (8mW/cm² @365 nm, 5 mins).

The reclaimed thiol-isocyanate resins were prepared by speed-mixingIrgacure 907 (1.2 wt % with respect to thioester diisocyanate) withdevolatilized thiourethane oligomers and stoichiometric thioesterdiisocyanate for 90 sec. The homogenized mixture was cured under thesame conditions as the pristine samples (8 mW/cm² @365 nm for 10 mins,followed by a post-cure at 80° C. overnight).

The reclaimed disulfide containing thiol-ene resins were prepared bymixing devolatilized recycling oligomers with stoichiometric DSDAE (withpre-dissolved 1 mol % 1184). The mixture was polymerized under the samecondition as the pristine samples (8 mW/cm² @365 nm, 20 mins).

Photolithography Procedure

Micro-features from both pristine and recycled monomers were prepared bycontact liquid photolithography. Irradiation was performed by acollimated UV light (50 mW/cm² @365 nm) through a photomasks (100 μmcircles separated by 100 μm screening gaps). Pristine samples comprisedstoichiometric PETMP-TEDAE monomers with 0.5 wt % 1184 and 0.3 wt %methylhydroquinone, and were irradiated for 120 sec. Recycled samplescomprised stoichiometric recycled oligomers and TEDAE, with 0.5 wt %1184 and 0.3 wt % methylhydroquinone (both with respect to unreactedmoieties), and were irradiated for 80 sec. Immediately afterirradiation, the unreacted compounds were washed away with ethanol.

Synthesis of thioester 1 (TE1): To a 1.00 L round-bottomed flaskequipped with a magnetic stir bar was added 50.0 g (500 mmol, 1.00equiv) of succinic anhydride which was diluted with 450 mL of anhydrousacetonitrile followed by 50.0 mL of anhydrous pyridine (1.00 M totalconcentration, 9:1 v/v ratio, MeCN:pyridine) and stirred for ˜5 minutesat room temperature to form a homogenous solution. Then, 43.5 mL (53.0g, 500 mmol, 1.00 equiv) of 3-mercatopropionic acid was added in asingle portion followed by 3.05 g (24.98 mmol, 0.05 equiv, 5.00 mol %)of DMAP. The reaction vessel was then sealed with a yellow cap under airand stirred at room temperature overnight (˜12 hours). After this periodthe reaction mixture was concentrated to a thick residue which wasdissolved in ˜1.00 L of ethyl acetate (EtOAc), acidified with a 1 Naqueous HCl solution (to pH=1), and the aqueous layer was back-extractedwith additional portions of EtOAc (250 mL, 2×); the combined organicswere dried over Na₂SO₄, filtered, and concentrated. Note: a smallerversion of this work-up procedure can be employed to check theconversion of this reaction before final work-up of the larger batch.The white solid obtained after evaporation of the solvent was dissolvedinto a minimal amount of dichloromethane (DCM, ˜100 mL) with rapidstirring using a football shaped magnetic stir bar and mild heating witha heat gun; after complete dissolution, the desired product wasprecipitated using a large excess of hexanes (˜1.00 L) which was addedsteadily to the stirring mixture. Filtration of the precipitatedmaterial and additional washes with smaller portions of hexanes (˜250mL, 2×) yielded 94.6 grams (92% yield) of the title compound (TE1) as awhite solid which was used in all subsequent studies with no furtherpurifications. This reaction has been successfully scaled up to a 1.00mole scale (100 g of the succinic anhydride employed) with no changes inthe stoichiometry, relative concentrations, reaction times, or work-up,which gave no significant changes in purity or yield of the finalproduct.TE1: 92% yield; white solid; R_(f)=n/a; ¹H NMR (400 MHz, MeOD-d₃, 25°C.): δ=3.09 (t, J=5.4 Hz, 2H), 2.87 (t, J=5.4 Hz, 2H), 2.63-2.56 (m,4H); ¹³C NMR (100 MHz, MeOD-d₃, 25° C.) 199.32, 175.57, 175.19, 39.34,35.08, 29.72, 24.87.

Synthesis of thioester 2 (TEDAE/TE2): To a 250 mL round-bottomed flaskequipped with a magnetic stir bar was added 10.0 g (48.5 mmol, 1.00equiv) of TE1 (synthesis of which is detailed above), 13.8 grams (97.0mmol, 2.00 eq) of anhydrous sodium sulfate (Na₂SO₄), 922 mg (4.85 mmol,0.10 equiv, 10.0 mol %) of p-toluenesulfonic acid monohydrate (TsOH—H₂O)and diluted with 100 mL (0.50 M) of reagent grade toluene. To thisstirring suspension, 13.2 mL (11.3 g, 194 mmol, 4.00 equiv) of allylalcohol was added in a single portion via pipette; the flask wasequipped with a reflux condenser (open to air), placed into an oil bath,and heated to 85° C. with rapid stirring for 12 hours. After this timethe reaction mixture was allowed to cool to room temperature and thesolids were filtered, the filter cake was washed with additionalportions of reagent grade toluene (25 mL, 2×), and concentrated to yielda clear syrupy residue (bath was placed at 60° C. to remove any tracesof excess allyl alcohol). The crude residue was directly submitted tocolumn chromatography (10%→20%→30% EtOAc/hexanes) and concentration ofthe fractions containing the desired material (R_(f)=0.19, TLCconditions: 10% EtOAc/hexanes) yielded 10.9 grams (79% yield) of thetitle compound (TEDAE) as a clear oil which was found to be sufficientlypure and was used in all subsequent studies with no furtherpurifications.TEDAE: 82% yield; non-viscous, clear oil; R_(f)=0.19 (TLC conditions:10% EtOAc/hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=5.95-5.85 (m,2H), 5.34-5.21 (m, 4H), 4.60-4.57 (m, 4H), 3.14 (t, J=5.4 Hz, 2H), 2.89(t, J=5.4 Hz, 2H), 2.70-2.63 (m, 4H); ¹³C NMR (100 MHz, CDCl₃, 25° C.)197.56, 171.66, 171.39, 132.03, 132.01, 118.66, 118.60, 65.65, 65.61,38.48, 34.45, 29.21, 24.07.

Synthesis of diallylester control (DAEC): To a 250 mL round-bottomedflask equipped with a magnetic stir bar was added 10.0 grams (57.4 mmol,1.00 equiv) of suberic acid, 16.3 grams (115 mmol, 2.00 eq) of anhydroussodium sulfate (Na₂SO₄), 1.09 grams (5.74 mmol, 0.10 equiv, 10.0 mol %)of p-toluenesulfonic acid monohydrate (TsOH—H₂O), and this was dilutedwith 115 mL (0.50 M) of reagent grade toluene. To this stirringsuspension, 15.6 mL (13.3 g, 230 mmol, 4.00 equiv) of allyl alcohol wasadded in a single portion via pipette; the flask was equipped with areflux condenser (open to air), placed into an oil bath, and heated to85° C. with rapid stirring for 12 hours. After this time the reactionmixture was allowed to cool to room temperature and the solids werefiltered, the filter cake was washed with additional portions of reagentgrade toluene (25 mL, 2×), and the filtrate was concentrated to yield aclear syrupy residue (bath was placed at 60° C. to remove any traces ofexcess allyl alcohol). The crude residue was dissolved in EtOAc (˜200mLs), transferred to a 500 mL separatory funnel, washed with an aqueoussolution of NaHCO₃(˜100 mLs, 2×), then brine (˜100 mLs, 1×). Thecombined organics were dried over Na₂SO₄, filtered, and concentrated toyield 12.6 grams (86% yield) of the title compound (DAEC) as a clear oilwhich was found to be sufficiently pure and was used in all subsequentstudies with no further purifications. Note: often the material wouldhave a small amount of an unknown precipitate suspended in the oil whichcould be easily removed by filtering the oil through a 0.2 μm syringefilter.DAEC: 86% yield; non-viscous, clear oil; R_(f)=0.33 (TLC conditions: 10%EtOAc/hexanes, visualized by KMnO₄ stain); ¹H NMR (400 MHz, CDCl₃, 25°C.): δ=5.96-5.86 (m, 2H), 5.33-5.21 (m, 4H), 4.58-4.56 (m, 4H), 2.32 (t,J=7.42 Hz, 4H), 1.67-1.60 (m, 4H), 1.38-1.30 (m, 4H); ¹³C NMR (100 MHz,CDCl₃, 25° C.) 132.42, 118.27, 65.10, 34.28, 28.87, 24.86.

HABI-1: To a 500 mL round-bottomed flask equipped with a magnetic stirbar was added 5.00 grams (32.1 mmol, 1.00 equiv) of2-chloro-4-hydroxybenzaldehyde which was diluted with 75.0 mL (0.43 M)of reagent grade DMF. To this stirring solution was added 7.52 mLs (10.0grams, 41.7 mmol, 1.30 equiv) of 1-iodooctane, 13.3 grams (96.3 mmol,3.00 equiv) of potassium carbonate (K₂CO₃), and this suspension washeated to 120° C. for 16 hours. After this time the suspension wasallowed to room temperature and the solids were filtered, the filtercake was washed with additional small portions of EtOAc (˜25.0 mLs, 3×),and the filtrate was concentrated to yield an orange residue. The cruderesidue was dissolved in EtOAc (˜200 mLs), transferred to a 500 mLseparatory funnel, washed with water (˜100 mLs, 2×), then brine (˜100mLs, 1×). The combined organics were dried over Na₂SO₄, filtered, andconcentrated to dryness. This crude residue was directly submitted tocolumn chromatography (0% 5% 10% EtOAc/hexanes) and the fractionscontaining the desired compound (R_(f)=0.30, TLC conditions: 10%EtOAc/hexanes) were concentrated to yield 7.84 grams (91%) of the titlecompound as a slightly yellow oil.HABI-1: 91% yield; slightly yellow oil; R_(f)=0.30 (TLC conditions: 5%EtOAc/hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=10.32 (d, J=0.82 Hz,1H), 7.88 (d, J=8.73, 1H), 6.92 (d, J=2.38, 1H), 6.87 (ddq, J=8.7, 2.4,0.9, 0.8, 1H), 4.02 (t, J=6.55, 2H), 1.83-1.76 (m, 2H), 1.49-1.41 (m,2H), 1.39-1.24 (m, 8H), 0.89 (t, J=6.79, 3H); ¹³C NMR (100 MHz, CDCl₃,25° C.): δ=188.73, 164.40, 139.87, 131.12, 125.93, 115.78, 114.18,68.98, 31.92, 29.39, 29.33, 29.06, 26.03, 22.79, 14.24.

HABI-2: To a 250 mL round-bottomed flask equipped with a magnetic stirbar was added 7.84 grams (29.2 mmol, 1.00 equiv) of HABI-1, which wasdissolved in 115 mLs (0.25 M) of glacial acetic acid. To this clearsolution was added 6.14 grams (29.2 mmol, 1.00 equiv) of benzil,followed by 19.1 grams (249 mmol, 8.50 equiv) of ammonium acetate toform a suspension. The flask was equipped with a reflux condenser,placed under a mild vacuum for ˜5 minutes, then opened to an atmosphereof argon; this procedure was repeated 3× times. The suspension was thenheated to 120° C., forming a solution at ˜100° C., and allowed to heatat this temperature for 16 hours. After this period the reaction mixturewas allowed to cool to room temperature and the volatiles were removedunder reduced pressure to give a crude residue. This residue wasdissolved in DCM (˜200 mLs), transferred to a 500 mL separatory funnel,washed with an aqueous solution of NaHCO₃(˜100 mLs, 2×), and brine (˜100mLs, 1×). The combined organics were dried over Na₂SO₄, filtered, andconcentrated to give 13.1 grams (98%) yield of the title compound as ayellow/beige solid which was found to be sufficiently pure forexperimental purposes and was utilized directly in the next step with nofurther purifications.HABI-2: 98% yield; yellow/beige solid; R_(f)=0.30 (TLC conditions: 10%EtOAc/hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=10.08 (bs, 1H), 8.34(d, J=8.75 Hz, 1H), 7.67 (bs, 2H), 7.48 (bs, 2H), 7.42-7.24 (bm, 6H),3.99 (t, J=6.55, 2H), 1.80 (m, 2H), 1.51-1.43 (m, 2H), 1.40-1.26 (m,8H), 0.90 (t, J=6.73 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃, 25° C.) 159.87,143.60, 131.92, 130.45, 129.08, 128.48, 127.88, 127.24, 127.10, 120.69,116.01, 114.45, 77.36, 77.36, 68.64, 31.95, 29.47, 29.37, 29.24, 26.12,22.81, 14.26.

Precautions were taken to conduct this synthesis in the absence of anyUV-light.HABI-O-noct: To a 250 mL round-bottomed flask equipped with a magneticstir bar and a 60.0 mL addition funnel was added 1.00 grams (2.18 mmol,1.00 equiv) of HABI-2 and this was diluted with 31.0 mLs (˜0.02 M) ofreagent grade benzene. To a separate 100 mL round-bottomed flaskequipped with a magnetic stir bar was added 2.44 grams (43.6 mmol, 20.0equiv) of KOH, diluted with 31.0 mLs (˜0.02 M, total dilution of ˜0.04M) of distilled water, and allowed to stir for ˜10 minutes or until thesolids had completely dissolved. After this period, 7.18 grams (21.8mmol, 10.0 equiv) of potassium ferricyanide (K₃[Fe(CN)₆]) was added in asingle portion and allowed to stir for an additional ˜10 minutes oruntil the solids had completely dissolved. The fully homogenousKOH/K₃[Fe(CN)₆] solution was placed into the 60.0 mL addition funnel,washing with minimal amounts of water to assure complete transfer of thereagents. The entire flask was placed under a mild vacuum and opened toan atmosphere of argon (balloon, 1 atm), this procedure was repeated 3times, keeping the argon filled balloon equipped to the reaction afterthe final cycle. The KOH/K₃[Fe(CN)₆] solution was then slowly addeddropwise to the reaction with vigorous stirring over the course of 30minutes. It was noted during this period that the biphasic reactionturned from a light-yellow solution into a bright blue/green biphasicsolution upon complete addition of the reagents. The reaction waswrapped in tin foil and allowed to stir vigorously for 16 hours at roomtemperature. After this period the reaction was transferred to a 250 mLseparatory funnel, the aqueous layer was removed and the organics werewashed with distilled water (˜100 mLs, 2×), brine (˜100 mLs, 1×), driedover Na₂SO₄, filtered, and concentrated to yield a crude yellow/bluefoam. The crude residue was directly submitted to column chromatography(5%→10% EtOAc/hexanes) and concentration of the fractions containing thedesired material (R_(f)=0.20, TLC conditions: 10% EtOAc/hexanes) yielded993 grams (99% yield) of the title compound (HABI-O-noct) as a clear oilwhich was found to be sufficiently pure and was used in all subsequentstudies with no further purifications. HABI-O-noct: 99% yield; yellowfoam; R_(f)=0.20 (TLC conditions: 10% EtOAc/hexanes); ¹H NMR (400 MHz,CDCl₃, 25° C.): δ=7.62 (d, J=8.3 Hz, 3H), 7.55 (t, J=7.4 Hz, 1H), 7.43(dd, 15.5, 7.4 Hz, 4H), 7.38-7.33 (m, 1H), 7.20-7.04 (m, 9H), 6.77-6.74(m, 2H), 6.57 (d, J=8.9, 1H), 6.41 (d, J=8.9 Hz, 1H), 6.01 (dd, J=8.9,2.6 Hz, 1H), 3.83-3.78 (m, 2H), 3.73-3.61 (m, 2H), 1.69 (p, J=7.1 Hz,4H), 1.43-1.26 (m, 20H), 0.93-0.86 (m, 6H); ¹³C NMR (100 MHz, CDCl₃, 25°C.) 168.13, 165.05, 159.63, 159.53, 144.16, 138.21, 135.34, 135.25,134.80, 133.22, 132.31, 132.28, 131.06, 131.00, 130.00, 129.95, 129.67,129.10, 128.40, 127.86, 127.77, 127.74, 127.61, 127.11, 126.98, 126.88,126.08, 116.89, 114.55, 113.08, 112.06, 110.80, 68.38, 68.22, 31.98,31.93, 29.50, 29.42, 29.40, 29.36, 29.21, 29.07, 26.19, 26.02, 22.83,22.78, 14.27, 14.24.

Synthesis of the TMG-appended photobase (PB): To a 100 mL round-bottomedflask equipped with a magnetic stir bar was added 2.00 grams (8.23 mmol,1.00 equiv) of 2-(2-nitrophenyl)propyl chloroformate (˜95% pure,obtained from Sigma-Aldrich) and diluted with 40.0 mLs (0.20 M) ofreagent grade DCM. This stirring solution was cooled to 0° C. by theapplication of an ice bath and 1.03 mLs (946 mgs, 8.21 mmol, 2.00 equiv)of 1,1,3,3-tetramethylguanidine (TMG). This clear solution was allowedto stir for 1 hour at 0° C., then the ice bath was removed and thereaction was allowed to stir for 16 hours. After this period thereaction was quenched by the addition of brine (˜50.0 mLs), transferredto a separatory funnel, washed with additional portions of brine (˜50.0mLs, 2×), and the combined organics were dried over Na₂SO₄, filtered,and concentrated to dryness. This crude residue was directly submittedto column chromatography (0%→1%→5% MeOH/DCM) and the fractionscontaining the desired compound (R_(f)=0.47, TLC conditions: 10%MeOH/DCM) were concentrated to yield 1.29 grams (98%) of the titlecompound (PB) as a slightly yellow oil. This oil was found to havesolidified as a waxy off-white solid after several hours of cooling in a−20° C. freezer. Alternatively, seeding this viscous oil with a smallquantity of a previously crystallized batch of NPPOC-TMG also greatlyaccelerated the speed of solidification.PB: 98% yield; waxy off-white solid; R_(f)=0.47 (TLC conditions: 10%MeOH/DCM); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=7.76-7.73 (m, 1H),7.57-7.52 (m, 2H), 7.35-7.31 (m, 1H), 4.29 (d, J=7.16 Hz, 2H), 3.75-3.68(m, 1H), 2.82 (s, 12H), 1.38 (d, J=6.94 Hz, 3H); ¹³C NMR (100 MHz,CDCl₃, 25° C.) 166.29, 160.29, 150.45, 138.49, 132.64, 128.58, 127.08,68.49, 39.85, 34.01, 18.72.

Synthesis of the photo-acid precursor (PA-OH): To a 100 mLround-bottomed flask equipped with a magnetic stir bar was added 5.00grams (33.1 mmol, 1.00 equiv) of 1-ethyl nitrobenzene using a Pasteurpipette and this was diluted with 30 mLs of reagent grade DMSO. To aseparate 20 mL scintillation vial equipped with a magnetic stir bar wasadded 1.49 grams (49.7 mmol, 1.50 equiv) of paraformaldehyde followed by929 mgs (8.27 mmol, 0.25 equiv, 25.0 mol %) of potassium tert-butoxide(KOtBu) and these were suspended in 9.00 mL of tert-butanol (t-BuOH). Tothis stirring suspension, 6.00 mLs of reagent grade DMSO was added andthe suspension formed a not fully clear but manageable (easilytransferrable) solution. This solution was pipetted into the stirringDMSO solution containing 1-ethyl-2-nitrobenzene (45 mLs total, totalconcentration 0.75 M, 4:1 DMSO/t-BuOH) and the reaction mixture wasstirred at room temperature for 16 hours. After this period the reactionwas diluted with water (˜50 mLs), transferred to a separatory funnel,and extracted with EtOAc (˜100 mLs, 2×). The combined organic layer waswashed with water (˜100 mLs, 2×), then brine (˜100 mLs, 1×), dried overNa₂SO₄, filtered, and concentrated to dryness. This crude residue wasdirectly submitted to column chromatography (10%→20%→30% EtOAc/hexanes)and the fractions containing the desired compound (R_(f)=0.25, TLCconditions: 30% EtOAc/hexanes) were concentrated to yield 5.66 grams(94%) of the title compound (PA-OH) as a yellow/orange oil which wasfound to be sufficiently pure and was used in all subsequent studieswith no further purifications.PA-OH: 94% yield; yellow/orange oil; R_(f)=0.25 (TLC conditions: 30%EtOAc/hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=7.77 (dd, J=8.14,1.37 Hz, 1H), 7.62-7.58 (m, 1H), 7.52 (dd, J=7.94, 1.49 Hz, 1H), 7.38(ddd, J=7.27, 1.49 Hz, 1H), 3.86-3.76 (m, 2H), 3.58-3.50 (m, 1H), 1.70(bs, 1H), 1.35 (d, J=6.92 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃, 25° C.)150.83, 138.21, 132.79, 128.31, 127.33, 124.24, 68.01, 36.49, 17.69.

Synthesis of the photo-acid (PA): To a 100 mL round-bottomed flaskequipped with a magnetic stir bar was added 1.00 grams (5.52 mmol, 1.00equiv) of PA-OH and this was diluted with 20.0 mLs (0.30 M) of reagentgrade DCM. To this was added 902 mgs (6.63 mmol, 1.20 equiv) ofphenylacetic acid, 34.0 mgs (0.28 mmol, 0.05 equiv, 5.00 mol %) of DMAP,and this suspension was allowed to stir for ˜10 minutes until it becamea solution. The reaction was then added 1.04 mLs (836 mgs, 6.62 mmol,1.20 equiv) of diisopropylcarbodiimide (DIC) was added dropwise; thereaction mixture was allowed to slowly warm to room temperature and stirfor 16 hours. After this period a fine precipitate had formed which wasvacuum filtered through a filter paper-topped Buchner funnel, washedwith additional small portions of DCM (˜10.0 mLs, 2×), and the combinedfiltrate was concentrated to give a cloudy thick residue. This residuewas dissolved in a minimal amount of EtOAc (˜20.0 mLs) and, again,filtered through a filter paper-topped Buchner funnel. The combinedfiltrate was concentrated to give an almost clear residue which wasdirectly submitted to column chromatography (5% 10% EtOAc/hexanes) andthe fractions containing the title compound (R_(f)=0.22, TLC conditions:10% EtOAc/hexanes) were concentrated to give 1.64 grams (99%) of thetitle compound (PA) as a slightly yellow oil which was found to besufficiently pure and was used in all subsequent studies with no furtherpurifications.PA: 99% yield; slightly yellow oil; R_(f)=0.22 (TLC conditions: 10%EtOAc/hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=7.74 (ddd, J=8.1,1.4, 0.4 Hz, 1H), 7.52-7.45 (m, 1H), 7.37-7.22 (m, 5H), 7.19-7.15 (m,2H), 4.28-4.20 (m, 2H), 3.70 (h, J=7.0 Hz, 1H), 3.55 (d, J=2.9 Hz, 2H),1.30 (d, J=6.98 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃, 25° C.) 6=171.37,150.50, 137.30, 133.92, 132.70, 129.37, 128.66, 128.30, 127.50, 127.18,124.55, 68.60, 41.44, 33.15, 17.78.

Synthesis of TE3: To a 250 mL round-bottomed flask equipped with amagnetic stir bar was added 5.00 grams (24.3 mmol, 1.00 equiv) of TE1(synthesis of which is detailed above), 535 mgs (2.43 mmol, 10.0 mol %,0.10 equiv) of 2,6-di-tert-butyl-4-methylphenol (BHT), and was dilutedwith 80.0 mLs (˜0.30 M) of reagent grade DCM. To this suspension wasadded 148 mgs (1.22 mmol, 0.05 equiv, 5.00 mol %) of4-dimethylaminopyridine (DMAP), 232 mgs (1.22 mmol, 0.05 equiv, 5.00 mol%) of p-toluenesulfonic acid monohydrate (TsOH—H₂O), 5.02 mLs (5.08grams, 43.7 mmol, 1.80 equiv) of 2-hydroxyethyl acrylate (HEA), and thissuspension was allowed to stir for ˜5 minutes at room temperature.Finally, the reaction was initiated by the addition of 8.37 mLs (6.75grams, 53.5 mmol, 2.20 equiv) of N,N′-diisopropylcarbodiimide (DIC)which was added in a single portion via syringe. After complete additionof the DIC the suspension formed a clear solution and after a fewminutes a fine white solid was noted to precipitate (most likely DIU);this suspension was allowed to stir at room temperature overnight. Afterthis period the reaction mixture was filtered, the filter cake waswashed with small portions of EtOAc (˜10.0 mLs, 2×), and the filtratewas concentrated to give a milky residue. The residue was againsuspended in a small portion of EtOAc (˜20.0 mLs), filtered, the filtercake was washed with additional small portions of EtOAc (˜5.00 mLs, 2×),and the filtrate was reduced to yield a nearly clear residue. Thisresidue was directly submitted to column chromatography (10%→20%→30%EtOAc/hexanes), the fractions containing the desired material(R_(f)=0.45, TLC conditions: 50% EtOAc/hexanes) was added 8.80 mgs (1000ppm based on a 90% ideal yield) of BHT, and concentrated to yield 9.58grams (98% yield) of a the title compound (TE3) as a clear oil which wasfound to be sufficiently pure and was used in all subsequent studieswith no further purifications.TE3: 98% yield; slightly viscous, clear oil; R_(f)=0.45 (TLC conditions:50% EtOAc/hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.): δ=6.46 (dd, J=17.3,1.35 Hz, 2H), 6.16 (dd, J=17.3, 10.4 Hz, 2H), 5.91-5.88 (m, 2H),4.40-4.34 (m, 8H), 3.15 (t, J=7.0 Hz, 2H), 2.91 (t, J=6.8 Hz, 2H) 2.69(d, J=24.7 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃, 25° C.) 197.43, 171.77,171.47, 165.99, 165.98, 131.65, 131.63, 128.04, 62.63, 62.57, 62.25,62.24, 38.38, 34.31, 29.06, 24.00.Synthesis of TE4: The exact procedure outlined above for the synthesisof TE3 was utilized to form the thioester dimethacrylate (TE4) with nochanges other than changing 2-hydroxyethyl acrylate (HEA) for2-hydroxyethyl methacrylate (HEMA).TE4: 9.72 grams; 93% yield; slightly viscous, clear oil; R_(f)=0.31 (TLCconditions: 30% EtOAc/Hexanes); ¹H NMR (400 MHz, CDCl₃, 25° C.):δ=6.16-6.14 (m, 2H), 5.63-5.61 (m, 2H), 4.38-4.35 (m, 8H), 3.15 (t,J=7.01 Hz, 2H), 2.91 (t, J=7.18 Hz, 2H), 2.72-2.66 (m, 4H), 1.97 (s,6H); ¹³C NMR (100 MHz, CDCl₃, 25° C.) 197.41, 171.77, 171.47, 167.22,167.21, 135.99, 126.30, 126.28, 62.64, 62.58, 62.42, 62.41, 38.40,34.34, 29.08, 24.02, 18.43.

Synthesis of TEDIC: To a flame dried, 3-neck 500 mL round-bottomed flaskequipped with a magnetic stir bar, reflux condenser (middle neck), and amineral oil filled gas bubbler (connected to the top of the refluxcondenser) feeding into a stirring, saturated aqueous solution of sodiumbicarbonate (NaHCO₃), was added 25.0 grams (121 mmol, 1.00 equiv) of TE1and this was diluted with 400 mLs (0.30 M) of dry toluene under anatmosphere of argon at room temperature. To this suspension was added35.3 mLs (57.8 grams, 485 mmol, 4.00 equiv) of thionyl chloride viasyringe and the suspension was allowed to stir at room temperature for˜10 minutes. After this period, 936 μLs (887 mgs, 12.1 mmol, 0.10 equiv,10.0 mol %) of N,N-dimethylformamide (DMF) was added via syringe in asingle portion, the flask was equipped with an oil bath, and heated to50° C. Soon after the reaction had reached temperature, gas was noted tobegin evolving (SO₂ and HCl) and the suspension slowly began to form asolution. After approximately 4 hours it was noted that gas had ceasedevolving from the reaction (which is best seen from the aqueous sodiumbicarbonate receiving flask) and the suspension had formed a clearsolution. At this time the reaction mixture was cooled to roomtemperature and the volatiles were removed under reduced pressure atroom temperature to give a viscous, often yellow or light brown residue.Additional portions of dry toluene (˜50.0 mLs, 2×) were added to theresidue, concentrated, and opened to argon each time; this step wasperformed twice to completely rid the residue of any residual thionylchloride or related volatile byproducts. Due to the instability of theintermediate product, the obtained viscous oil was used immediately inthe next step with no further purifications assuming full conversion tothe anticipated product (121 mmol).

To a flame dried, 3-neck 500 mL round-bottomed flask under an atmosphereof argon, equipped with a magnetic stir bar, reflux condenser (middleneck), and 60 mL addition funnel (side neck) was added 17.4 grams (267mmol, 2.20 equiv) of sodium azide (NaN₃) and this was diluted with 120mLs (1.00 M) of dry acetonitrile (taking care to wash any NaN₃ from theside of the flask). The flask was then equipped with an oil bath andheated to 90° C. During the time it took to heat the suspension toreflux, the above obtained viscous oil (121 mmol, 1.00 equiv) wastransferred to the closed 60 mL addition funnel via cannula. Thisprocess was accomplished by placing the 3-neck receiving flask underslightly reduced pressure while keeping the other flask under a positivepressure of argon; several additional small washes of the flaskcontaining the thioester diacid chloride with MeCN were performed andtransferred via cannula to the addition funnel using the same procedure.Once the oil bath had equilibrated and the NaN₃ suspension had begunrefluxing, the solution containing the thioester diacid chloride wasslowly added dropwise over the course of 2 hours, which resulted in theimmediate and often intense formation of gas (N₂). The addition of thethioester diacid chloride to the sodium azide results in the exothermicand violent formation of gas. This addition should be monitored andperformed slowly over the course of approximately 2 hours to maintain acontrolled reaction.

Soon after concluding the addition of the thioester diacid chloride theevolution of gas had ceased and the reaction mixture was noted to haveturned a deep brown with a fine precipitate (predominately NaCl withsome residual NaN₃). At this point the reaction was removed from theheating source and allowed to cool to room temperature. Filtration ofthe precipitated solid through a Buchner funnel equipped with a paperfilter and additional small washes of the solid with dry MeCN (˜5 mLs,3×) gave a deep brown filtrate which was concentrated under reducedpressure to yield a low viscosity brown oil. Although ¹H-NMR, ¹³C-NMR,and IR revealed only the existence of the desired product, which whencompared to an internal standard (1,3,5-trimethoxybenzene) gave a purityof >95%, the deep brown color was undesirable for use in neat resins. Inorder to rid the material of this color, the residue was placed into a60.0 mL speed mixer cup and anhydrous magnesium sulfate (MgSO₄) wasadded to the mixture with intermittent speed mixed (˜2000 rpm) until adamp, sand-like mixture was obtained.

This material was placed into a Soxhlet thimble and lowered into aSoxhlet extractor connected to a 1.00 L round bottomed flask equippedwith a magnetic stir bar, —1.00 grams of activated charcoal, and 500 mLsof reagent grade hexanes. The Soxhlet extractor was further equippedwith a reflux condenser, the lower round bottomed flask was heated toreflux (75° C.), and the MgSO₄ mixture was allowed to be continuouslyextracted for 16 hours. After this time, it was noted that the sand-likeMgSO₄ mixture was essentially free flowing and all of the TEDIC had beenextracted. The receiving flask was then removed from the heat, allowedto cool to room temperature, filtered through a small pad of celite(packed with DCM), and washed with small portions of DCM (˜20 mLs, 3×).The clear filtrate was concentrated under reduced pressure to yield 21.1grams (87%, over 2 steps) of the title compound (TEDIC) as clear orslightly yellow low viscosity oil which was utilized directly with nofurther purifications. TEDIC: 87% yield; clear to yellow oil; R_(f)=n/a;¹H NMR (400 MHz, CDCl₃, 25° C.): δ=3.65 (t, J=6.20 Hz, 2H), 3.50 (t,J=6.25 Hz, 2H), 3.17 (t, J=6.51 Hz, 2H), 2.88 (t, J=6.37 Hz, 2H).

A wide range of additional thioester monomers can be readily derivedfrom the TEDIC monomer though procedures which would be known to thoseof ordinary skill in the art. Below is a scheme depicting of exemplarythioester monomers which can be derived from the TEDIC monomer core.

Characterizations Fourier Transform Infrared Spectroscopy (FT-IR)

FT-IR spectra and reaction kinetics were obtained on a Nicolet 670.Samples placed between two glass slides (for thiol-ene systems) with0.08 mm thick spacers, or between salt plates (for thiol-isocyanatesystems). An Acticure 4000 lamp equipped with a 365 nm bandpass filterwas used as light source. The conversions were determined by thedecrease in peak area centered at 3085 cm⁻¹, 2570 cm⁻¹ and 810 cm⁻¹ forallyl ehter, thiol and isocyanate, respectively.

Dynamic Mechanical Analysis (DMA)

DMA experiments were conducted on a TA Instruments Q800. Samples werecut into strips with approximate dimensions of 10×6×0.25 mm. Temperaturewas ramped at 3° C./min from −80° C. to 80° C. for rubbery samples,while from 20° C. to 150° C. for glassy materials, at a frequency of 1Hz. The glass transition temperature (Tg) was assigned as the peak ofthe tan δ curve.

Tensile Test

A tensile tester with a 500 N load cell (MTS Corp., Eden Prairie, Minn.)was used to measure modulus for polythiourethane samples. Dog-boneshaped (ASTM D638-V, dimension 63.5 mm×9.5 mm×0.25 mm) samples wereprepared by cutting from a 0.25 mm thick sample sheet. The samples werepulling at a rate of 0.75 mm/min.

Gel Permeation Chromatography (GPC)

The molecular weight and distribution were obtained by gel permeationchromatography (Tosoh EcoSEC HLC-8320). Dimethyl sulfoxide was used asthe eluting solvent at 0.35 mL/min at 50° C. A refractive index detectorwas used, calibrated by PMMA standards.

Rheology

The viscosity of the recycled oligomer was measured on a TA instrumentsARES rheometer. The liquid oligomers were placed between quartz plates(20 mm diameter, gap 0.1 mm). All oligomers behaved as Newtonian fluidsin the detectable torque ranges.

Thermogravimetric Analysis (TGA)

The weight loss of polymer samples was obtained on a Perkin-ElmerPyris 1. Sample filled platinum pans (—10 mg of samples) were heatedfrom 55 to 800° C. at 10° C./min under nitrogen flow.

Rheometry

Frequency sweeps were performed on an ARES rheometer (TA instruments)with a temperature controlled stage installed, which served as thebottom plate under the sample. For the top plate, an 8 mm diameterquartz plate was used, with a mirror on the top fixture that directedlight from a light guide through the sample. Quartz was employed ratherthan a standard metal plate to allow for irradiation of the sample topolymerize in situ, as well as to minimize temperature gradients throughthe sample. The polymerization was initiated using a mercury arc lamp(Acticure, EXFO) using a 365 nm filter and a light intensity of 3mW/cm². During irradiation, the storage and loss moduli were monitored,using a constant strain of 5% and frequency of 5 rad/s. The time scanwas stopped and lamp turned off once the modulus had reached a plateauvalue. Once the polymerization was completed, the temperature wasequilibrated to the desired value and frequency scans were performedusing between 1-5% strain over several orders of magnitude of frequency.

Computational Studies

Calculations were performed with Gaussian 09 computational chemistrypackage, using Trestles Supercomputer, XSEDE. Stationary geometries(reactants, transition states and products) were computed for allsystems studied using density functional theory based on the M06 densityfunctional and 6-31+G** basis set. The M06 functional was chosen becauseit has been parameterized with experimental thermodynamic data, shouldprovide a reliable description of the molecular structures for thereactions of interest. An adequate treatment of solvent is crucial tocorrectly describe reactions involving a polar TS, such as thoseinvolving nucleophilic attacks, which are of interest here. Therefore,the implicit polarized continuum solvation model (CPCM) was employed inall calculations to treat the solute-solvent electrostatic interactions.The modeled solvent was chosen as ethyl acetate to approximate themonomer/polymer environment containing ester functionality. Vibrationalforce constants were calculated at the M06/6-31+G** level of theoryto: 1) verify that the reactant and product structures have onlypositive vibrational modes, 2) confirm that each TS has only oneimaginary mode and that it connects the desired reactant and productstructures via Intrinsic Reaction Coordinate (IRC) calculations, and 3)compute entropies, zero-point energies (ZPE) and thermal correctionsincluded in the reported free energies at 298K.

Example 1: Preparation of Covalent Adaptable Networks for RapidThiol-Thioester Exchange at Ambient Temperature

A solvent-free thiol-ene networks was prepared via rapidphotopolymerization on demand, while preserving a high free thiolconcentration as needed to participate in exchange reactions after thepolymerization is complete. The thioester-containing diene monomer,TEDAE (FIG. 2 ), is a low-viscosity, transparent liquid and can besynthesized in good yield by a two-step process (see Materials andMethods section). The Flory-Stockmayer predicted gel point for a networkcontaining a tetrafunctional thiol and a diene with a 2:1 thiol:eneratio is 82%; the “click” nature of the thiol-ene reaction ensures thatquantitative conversion of the allyl ester is reached after only secondsof irradiation in thin films, so that gelation is achieved rapidly andreliably. The resulting films are low crosslinking density, low T_(g)rubbers (FIG. 3 ). Liquid organic bases such as TEA, PMDETA, and DBUshowed excellent solubility in the resins at the concentrations tested.Besides causing a slight decrease in modulus due to plasticization, thebase catalysts generally had little impact on the polymerization or thefilm itself. DBU was observed to slow down the polymerization rate, buta similar modulus to the other formulations was achieved after extendedlight exposure (FIG. 4 ).

For thiol-thioester exchange to occur in networks, three elements arenecessary: free thiol groups, a catalyst to deprotonate the thiol, andthe thioester moiety. As demonstrated by creep experiments (FIG. 5 ),networks deficient in any one of these three components behaved astypical crosslinked elastomers with a recoverable compliance close tozero after 20 minutes recovery time. When thioester, free thiol, andbase catalyst are all present, however, the material's creep behaviorresembles that of an entangled polymer melt, with a linear increase increep compliance with time and an equilibrium compliance of around 2.4MPa⁻¹, as measured after 20 minutes of strain recovery (FIG. 5 ). Insilico experiments revealed that the activation energy of a protonatedaliphatic thiol attacking an aliphatic thioester was about 33.6kcal/mol; however, if the thiol was deprotonated the activation energydropped significantly to 4.3 kcal/mol (FIG. 6 ). An analogous trend inactivation energies was observed for alcohol-ester exchange, but becausethiols are much more easily deprotonated than analogous alcohols,thiol-thioester exchange reactions are more accessible at lowtemperatures as compared with corresponding transesterificationreactions. If no base catalyst is present, the thiol-thioester exchangenetworks do exhibit stress relaxation at high temperatures (FIG. 7 ),where sufficient energy is present in the system to overcome the kineticbarriers for the exchange of protonated thiols and thioesters.

Without being limited to any theory, because the activation energy ofthe exchange is low and the thiolate anion is regenerated following eachexchange event, it follows that only a small percentage of thiol groupsneed to be deprotonated for significant bond reshuffling and consequentstress relaxation to take place. The choice of catalyst and loadinglevels determine the concentration of thiyl radicals within the network,which in turn affects the rate of the exchange reaction and thecharacteristic stress relaxation times. FIG. 8A shows the effect of thePMDETA concentration on stress relaxation. The relaxation time decreasedby a factor of approximately two when the catalyst concentration wasdoubled (FIG. 8B), suggesting a near-first order dependence. Frequencysweep data in shear (FIG. 9 ) revealed storage and loss modulus profilesreminiscent of an entangled linear polymer melt, where a local minimumin G″ is observed. With progressively stronger base catalysts, thestorage and loss modulus curves shift towards higher frequencies. Withthe strongest base tested, DBU, a G′-G″ crossover occurred within theobservable frequency range, which is a phenomenon usually observed inlinear polymer melts that can flow at sufficiently long time scales.When no catalyst is included, no local minimum in G″ is observed,typically indicating an irreversibly crosslinked elastomer.

Example 2: Use of Thiol-Thioester Exchange Networks in ImpressionMaterials and Nanoimprint Lithography at Ambient Temperatures

A potential application for thiol-thioester exchange networks is inimpression materials or nanoimprint lithography (NIL). A rubberythioester-containing film with excess thiol and base catalyst wasphotopolymerized, then nanoimprinted for 10 minutes at 40 bar pressureclose to ambient temperature, using a fluorinated silicon mold master(FIG. 10A). The silicon mold pattern had a feature height of 220 nm andperiod of 880 nm. Due to the high surface energy of the nanoscaletopology, the continuous bond reshuffling between thiols and thioesterscaused the pattern to gradually flatten over time, as evidenced byperiodic monitoring of the surface by AFM (FIGS. 10A-10B) and anobservation of optical changes visible to the eye (FIG. 10D). A controlfilm that did not contain any base catalyst showed no detectable patterntransfer or shape change.

Example 3: Development of “ON/OFF” Switch for Thiol-Thioester Exchange

Thiol-thioester exchange occurs at room temperature only when freethiols, thioesters, and a base catalyst are present. Therefore, dynamiccovalent network behavior can also be triggered “on” or “off” by theintroduction or elimination of any one of the three components from thematerial (FIG. 11 ). The use of light exposure to turn “on” or “off” theexchange reactions allows for spatiotemporal control and patterning ofdynamic behavior in polymer films. One method for providing an“off-switch” to bond rearrangement is to use a multi-stage cure with astoichiometric thiol-ene formulation. Because the thiol-ene reaction isradical-mediated, when the light is turned off, radicals rapidlyterminate and the polymerization ceases. Thus, in the first-stageexposure of a stoichiometric formulation of the thiol-ene network, thedesired combination of thiol, thioester, and base, can be achieved wherethe polymer behaves as a crosslinked gel, but unreacted free thiolsremain available to participate in exchange reactions. Subsequent lightexposure, delivered at any time and location desired, completes thethiol-ene reaction, resulting in consumption of the remaining freethiols and preventing any additional network adaptation of stressrelaxation associated with thiol-thioester exchange process. Tensilestress relaxation experiments, performed on the film after the first-and second-stage exposures, respectively, revealed that dynamic behavioronly occurred in the partially-cured stoichiometric film, and only whenbase catalyst was present (FIG. 12A). Photopatterning of thesecond-stage cure was utilized in combination with nanoimprintlithography to create complex mixed-scale surface patterns, where onlythe areas that were not irradiated in the second-stage cure could adaptto the imprinted pattern (FIG. 12B). The nanoimprinted films wereflood-cured shortly after imprinting to “fix” the surface pattern beforeimaging.

An “on-switch” was sought in order to provide an additional level ofcontrol over dynamic behavior in thioester networks. In choosing aphotobase for this purpose, primary amines were avoided, since these areknown to react irreversibly with thioesters to form amide bonds, as isthe case in native chemical ligation. The photobase NPPOC-TMG, which isa nitrobenzyl-protected version of the strong organic base1,1,3,3-tetramethylguanidine, was initially chosen. NPPOC-protectedcompounds have a very low absorbance above 400 nm and can be deprotectedusing 320-390 nm wavelength light. Thus, the visible light sensitivephotoinitiator Irgacure 819 (1819) was included so that polymerizationcould be performed using 400-500 nm light, to avoid generating the baseprematurely. Creep experiments were performed before and after a UVexposure of the previously polymerized film (320-390 nm, 15 mW/cm², 10minutes). The results of the creep experiments (FIG. 4B) show thatsignificant creep was observed only after the UV exposure, indicatingthat the photodeprotection of a base catalyst represents an effectiveway to externally control bond reshuffling within the network.

Example 4: Preparation of Thioester Containing Network Polymers ViaPhotoinitiated Thiol-Ene Reaction

To a 10.0 mL speed mixer vial was added 250 mgs (0.87 mmol, 1.00 equiv)of TE1, 427 mgs (0.87 mmol, 1.00 equiv, “100% excess thiol”) ofpentaerythritol tetra(3-mercaptopropionate) (PETMP), and 36.4 μL (30.2mgs, 0.17 mmol, 0.20 equiv, 20.0 mol %) ofN,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) each via Pasteurpipettes. This clear resin was then manually mixed with a pipette tipfor ˜2 minutes to make a homogenous mixture. Following this,approximately 8.91 mgs (3.48×10⁻² mmol, 0.04 equiv, 4.00 mol %) of2,2-dimethoxy-2-phenylacetophenone (DMPA), which had been crushed withthe flat side of a spatula to form a fine powder, was added and theresin was further manually mixed with a pipette tip for an additional ˜2minutes to form a homogeneous mixture. At this time the clear resin waspoured between two glass slides treated with Rain-X (ITW Global Brands,Houston, Tex.) using 250 μm thick spacers (Small Parts Inc., Logansport,Ind.). The material was irradiated (365 nm, 5.00 μW/cm², roomtemperature) for ˜10 minutes to give the thiol excess thioestercontaining network polymer (FIG. 13 ). The conversion was found to beessentially quantitative by in situ IR, revealing complete consumptionof the “ene” species (FIG. 14A). Moreover, it was shown that, due to thequantitative nature of the thiol-ene reaction, any excess of eitherreactant (ene or thiol) is remained unreacted in the final networkpolymer (FIG. 14B). This procedure generally formed circular sampleswhich were cut utilizing a single edge straight razor blade to form therequired rectangular samples. Note: this represented the+thioester+base+free SH formulation utilized in FIG. 5 (black squares).

+thioester+base−free SH formulation: The representative procedureoutlined above was modified to a 2:1 ene:thiol ratio (as opposed to 1:2ene:thiol) to ensure that all free thiol was consumed and a similarcrosslinking density was preserved (FIG. 5 , redsquares)+thioester−base+free SH formulation: The representativeprocedure outlined above was utilized, however, PMDETA was not added tothe resin (FIG. 5 , blue upward triangles)−thioester+base+free SHformulation: The representative procedure outlined above was utilized,however, tri(ethylene glycol) divinyl ether (CAS: 765-12-8), whichcontained no thioester linkage, was employed in the stead of TE1;relative stoichiometry of ene:thiol (1:2) was maintained (FIG. 5 , greendownward triangles).

The network containing free thiol, thioester, and a weak organic base(PMDETA), rapidly underwent rearrangement at room temperature; the creepbehavior resembled that of an entangled polymer melt with a linearincrease in creep compliance with time and an equilibrium compliance of2.4 MPa⁻¹. Removal of any of these three components (thiol, thioester,or base) resulted in networks which behaved as typical cross-linkedelastomers with a recoverable compliance close to zero after a 20-minuterecovery time. Increasing the concentration of base (PMDETA, FIGS.8A-8B) resulted in more rapid rearrangement of the network, presumablydue to the proportionately higher concentration of thiolate present.Covalent attachment of the base (PMDETA) to the network did not affectthe ability of the network to relax stress (FIG. 15A-15B). Depending onthe rate at which the network was strained little to no stress was builtup within the polymer (FIG. 16 ). Heating the network increased the rateof stress relaxation, presumably due to increased kinetics of mobilityat higher temperatures (FIGS. 17A-17B).

Example 5: Formation of a Plano-Convex Lens from Recycled Polymer

To a 20.0 mL speed mixer vial was added 4.00 grams (13.9 mmol, 1.00equiv) of TE1, 6.82 grams (13.9 mmol, 1.00 equiv) of PETMP, 292 μLs (243mgs, 1.39 mmol, 0.10 equiv, 10.0 mol %) of PMDETA, and 58.0 mgs (0.14mmol, 0.01 equiv, 1.00 mol %) of IR819. This thick residue was manuallymixed with a pipette tip until all of the solids (IR819) had dissolvedand the clear, slightly yellow residue was loaded into a 16 mL syringeand pushed through a syringe filter (45.0 μm) into a 25.0 mL petri dish.This residue was allowed to settle at room temperature for approximately1 hour. After this period the dish was placed into a shallow ice bathand irradiated (405 nm, 50.0 mW/cm², room temperature) for 10 minutes.The now polymerized sample was allowed to reach room temperature andremoved from the petri dish (FIG. 18A).

The polymerized sample was cut into length-wise strips and then furthercut into small cubes to form “cut” material. This was done using asingle edge straight razor blade. A small amount of this cut sample wasutilized to show that the thiol-ene polymerization reaction had reachedfull conversion by FT-IR. (FIG. 18B)

A 60.0 mL plastic syringe, which had been soaked in isopropanol andsonicated for ˜1 hour, was loaded with the polymeric cut material. Theplunger was pressed down firmly to contact the cut material and severalrubber bands were wrapped around both ends of the syringe to furthercompress the material. This syringe was left at room temperature for 48hours (2 days) to form the puck of healed material. To remove the puck,the syringe was cut down the side and the puck was easily removed. (FIG.18C)

The healed material was placed on top of an optically flat surface(Optosigma BK-7, λ/10) and then a UV-fused silica plano-convex lens(Thorlabs, Ø½″, f=4.0 mm) was placed on top of the material followed bya lens cleaning tissue paper (Thorlabs). This sandwich of material wascompressed for three hours under mild pressure at room temperature. Uponremoval of the lens from the material a plano-concave lens was formedwhich, if not further imprinted upon, was indefinitely stable. (FIG.18D)

Example 6: Preparation of a Thioester Containing Network Polymers withDifferent Catalysts

To a 10.0 mL speed mixer vial was added 250 mgs (0.87 mmol, 1.00 equiv)of TEDAE, 427 mgs (0.87 mmol, 1.00 equiv, “100% excess thiol”) ofpentaerythritol tetra(3-mercaptopropionate) (PETMP), and varying basicor nucleophilic catalyst (0.03 mmol, 0.03 equiv, 3.00 mol %) each viaPasteur pipettes. This clear resin was then manually mixed with apipette tip for ˜2 minutes to make a homogenous mixture. Following this,approximately 8.91 mgs (3.48×10⁻² mmol, 0.02 equiv, 2.00 mol %) of2,2-dimethoxy-2-phenylacetophenone (DMPA), which had been crushed withthe flat side of a spatula to form a fine powder, was added and theresin was further manually mixed with a pipette tip for an additional ˜2minutes to form a homogeneous mixture. At this time the clear resin waspoured between two glass slides treated with Rain-X (ITW Global Brands,Houston, Tex.) using 250 μm thick spacers (Small Parts Inc., Logansport,Ind.). The material was irradiated (365 nm, 5.00 μW/cm², roomtemperature) for ˜10 minutes to give the thiol excess thioestercontaining network polymer.

The networks were formed essentially instantaneously via a thiol-enephotopolymerization (FIGS. 19A-19B), which allowed for screening ofvarious catalysts to observe their effect on the rate of exchange. Whileholding the concentration of each catalyst the same (3.0 mol %, ˜0.6 wt%), basic catalysts with varying pKa values (5.3-13.6) were evaluated bycomparing their normalized rates of stress relaxation (constant appliedstrain of 10%, 90 minutes, RT, FIG. 19A). More basic amines, such as DBUor TMG, were found to relax stress more rapidly than less basic amines,such as 4-tert-butylpyridine or Hunig's base. As the pKa of the freethiol in the network is approximated to be ˜10.4 (based on the pKa of3-methyl mercaptopropionate), only those above this threshold showedsignificant stress relaxation. Despite the expected requirement forthiolate generation, the apparent catalytic activity of DABCO (pka=8.8,3.0 mol %) to relax stress in the system was surprising as it is not astrong enough base to deprotonate the free thiol to a significant degreeunder most conditions. However, DABCO is a strong nucleophile (N=18.8,MeCN). The importance of nucleophilicity was corroborated by screeningcatalysts of relatively low basicity and high nucleophilicty in thepolymer system (FIG. 19B). Catalysts such as PPh₃ (N=13.6, MeCN) showedno discernable relaxation, whereas more nucleophilic catalysts such asDMAP, DABCO, and quinuclidine (N=15.5, 18.8, and 20.5, MeCN) showedincreasingly rapid relaxation in accordance to their nucleophilicity.Quinuclidine, the most potent nucleophile investigated, showed thehighest rate of relaxation, however, as it is also a modestly strongbase, it could potentially operate through both basic and nucleophilicmechanisms. Creep experiments showed that free thiol, thioester, and thenucleophilic catalyst were required for flow to occur within thenetwork; exclusion of any of these components resulted networks thatresembled typical cross-linked elastomers (FIG. 19A). Although TMGoutstripped all other catalysts to induce plasticity in the networks atambient temperatures (FIG. 19B), basic catalysts, such as DBU, wereshown by in situ IR to significantly retard the kinetics of thethiol-ene free radical polymerization at higher concentrations (FIG.20A), whereas, non-basic, nucleophilic catalysts, such as quinuclidine,did not (FIG. 20B). It is possible that deeper cures and indefinitelystable films are feasible utilizing non-basic, nucleophilic catalysts,such as quinuclidine or DABCO, as they do not perturb the opticalthickness of the resin nor do they form a significant amount of thiolatewhich can slowly form disulfide crosslinks.

Example 7: Preparation of a Thioester Network Containing a UV-ReleasableBase (“on Switch”)

To a 10.0 mL speed mixer vial was added 250 mgs (0.87 mmol, 1.00 equiv)of TEDAE, 427 mgs (0.87 mmol, 1.00 equiv, “100% excess thiol”) ofpentaerythritol tetra(3-mercaptopropionate) (PETMP), and 14.0 mgs (0.04mmol, 0.05 equiv, 5.00 mol %) of NPPOC-TMG (PB, FIG. 21 ). Thissuspension was then manually mixed with a pipette tip for ˜10 minuteswith mild heating and sonication to make a completely homogenousmixture. Following this, approximately 5.73 mgs (8.70×10⁻³ mmol, 0.01equiv, 1.00 mol %) of HABI-Cl was added and the resin was placed onto ahot plate set at 60° C. for ˜10 minutes with sporadic manually mixingusing a pipette tip until most of the HABI-Cl had dissolved. At thistime the cloudy yellowish resin was filtered through a cotton pluggedPasteur pipette onto a glass slide treated with Rain-X (ITW GlobalBrands, Houston, Tex.) using 250 μm thick spacers (Small Parts Inc.,Logansport, Ind.) which was sandwiched between another Rain-X treatedglass slide. The material was irradiated (455 nm, 30.0 μW/cm², roomtemperature) for ˜2-5 minutes to give the photobase containing networkpolymer (FIGS. 22A-22B). Irradiation of this resin with 455 nm lightgave rapid formation of the network (˜1 minute), which was noted to goto full conversion in the “ene” species (FIG. 23 ). The conversion wasfound to be essentially quantitative by IR, revealing completeconsumption of the “ene” species while an evident concentration of thiolremained.

Example 8: Temporally Controlled Stress Relaxation of a ThioesterContaining Network Polymer with a UV-Releasable Base (“on Switch”)

A small strip of fully cured material formed from a photoinitiatedthiol-ene polymerization (preparation detailed above) was placed ontothe DMA (TA Instruments RSA-G2) and a light guide equipped with acollimating lens attached to a mercury lamp (365 nm filter) was placedin close proximity (˜5.00 cm) to the front side of the sample. A stressrelaxation experiment was started and irradiation (365 nm, 75.0 mW/cm²,room temperature) of the sample took place 5 minutes, 10 minutes, and 15minutes after the experiment had begun. In each case the sample wascontinuously irradiated, once started, for the duration of theexperiment (30 minutes total).

Before further irradiation these networks acted as typical cross-linkedthermosets, showing essentially no stress relaxation over the course ofone hour, however, upon irradiation (365 nm, ˜75 mw/cm², 10 minutesafter experiment started, FIG. 24A) the basic catalyst was rapidlyreleased, partaking in thiol-thioester exchange and relaxing all stressin the network. Further evidence of temporal control over the release ofthe base was demonstrated by releasing the base 20 and 30 minutes afterstarting the experiment (FIG. 24B), in all three cases essentially allstress had been relaxed ˜5 minutes after beginning irradiation

Example 9: Preparation of a Thioester Network Containing a UV-ReleasableAcid (“Off Switch”)

To a 10.0 mL speed mixer vial was added 500 mgs (1.74 mmol, 1.00 equiv)of TEDAE, 849 mgs (1.74 mmol, 1.00 equiv, “100% excess thiol”) ofpentaerythritol tetra(3-mercaptopropionate) (PETMP), 2.20 μLs (2.02 mgs,1.74×10⁻² mmol, 0.01 equiv, 1.00 mol %) of TMG, and 26.0 mgs (8.70×10⁻²mmol, 0.05 equiv, 5.00 mol %) of NPPOC-phenylacetic acid (NPPOC-PAA, PA,FIG. 26 ) (FIGS. 28A-28B). The acid generating NPPOC-PAA was chosen dueto its desirable kinetics for the release of acid in solution uponexposure UV light (FIG. 28 ). This suspension was then manually mixedwith a pipette tip for ˜5 minutes with mild heating and vortexing tomake a completely homogenous mixture. Following this, approximately 63.6mgs (6.96×10⁻² mmol, 0.04 equiv, 4.00 mol %) of HABI-O-noct was addedand the resin was further manually mixed with a pipette tip for anadditional ˜5 minutes to form a homogeneous mixture (due to theincreased solubility of HABI-O-noct in the resin, when compared toHABI-Cl, only mild, intermediate heating and vortexing was required). Atthis time the yellowish resin was poured between two glass slidestreated with Rain-X (ITW Global Brands, Houston, Tex.) using 250 μmthick spacers (Small Parts Inc., Logansport, Ind.). The material wasirradiated (455 nm, 50.0 μW/cm², room temperature) for 8 minutes (4minutes each side, timed) to give the photo-acid containing networkpolymer. Irradiation of this resin with 455 nm light gave rapidformation of the network (8 minutes), which was noted to go to fullconversion in the “ene” species (FIG. 29 ). The conversion was found tobe essentially quantitative by IR, revealing complete consumption of the“ene” species while an evident concentration of thiol remained.

Example 10: Temporally Controlled Stress Relaxation of a ThioesterContaining Network Polymer with a UV-Releasable Acid (“Off Switch”)

A small strip of fully cured material formed from a photoinitiatedthiol-ene polymerization (preparation detailed above) was placed ontothe DMA (TA Instruments RSA-G2) and a light guide equipped with acollimating lens attached to a mercury lamp (320-500 nm filter) wasplaced in close proximity (˜5.00 cm) to the sample. A stress relaxationexperiment was started and irradiation (365 nm, 75.0 mW/cm², roomtemperature) of the sample took place 5, 20, and 60 seconds after thestress experiment had started. In each case the sample was continuouslyirradiated for 120 seconds and the light was turned off after thisperiod. The stress relaxation experiment was then run the remainder ofthe period (15 minutes total).

These samples aged significantly, decreasing in the rate of stressrelaxation as a function of time once polymerized. Therefore, only asmall portion of the material was polymerized at a time (placing theremaining bulk of the un-polymerized material into a −20° C. freezer). Astatic 10-minute aging period following polymerization was employed toallow for homogeneous aging across multiple runs. The sample was loadedonto the DMA during this aging period and the stress relaxationexperiment was started promptly at the end of this phase. Any leftoverpolymerized material was discarded. This procedure was repeated severaltimes to obtain the data shown in FIGS. 31A and 31B, placing the bulk ofthe un-polymerized material back into the −20° C. freezer in-betweenuse.

Example 11: Degradation and Recycling of CANs at Ambient Temperatures

Bond reshuffling reactions with fast kinetics at ambient conditionsallow for polymer recycling. In contrast to the present invention,thermosets cannot be readily dissolved or remolded once polymerized,leading to the disadvantage that thermosets are primarily single-use andnearly impossible to recycle or reuse. A chemoselective exchange, suchas the thiol-thioester reaction, addresses this issue by enabling anon-demand solution-based depolymerization of the network.Thiol-thioester exchange CANs can be completely dissolved within secondsby mercaptoethanol in the presence of a base catalyst (FIG. 33A) whereneither base nor residual thiol need to be initially present in therecyclable network. The large excess of monofunctional thiol from thesolution rapidly exchanges with network thioesters, forming end-cappedoligomers that then quickly dissolve. Following activation energytrends, no significant depolymerization was observed when either thethioester or the base catalyst was not present, or when ethanol was usedinstead of mercaptoethanol, even after 24 hours of soak time (FIG. 33B).These results suggest that thioester-containing polymers may bedissolved and recycled only when the correct conditions are introduced,otherwise behaving as an ideal, insoluble crosslinked network polymer.

Example 12: Preparation of Pristine Polymers for Degradation andRecycling

Stoichiometric thiol-ene polymerizations between tetra-thiol (PETMP) anddi-ene (TEDAE) monomers were used for the preparation of pristinepolymers, with a catalytic amount of photoinitiator (DMPA) added priorto UV light exposure. The thiol-allyl ether radical polymerizationproceeded rapidly and generated optically clear, colorless and tack-freefilms, after just seconds of irradiation. As illustrated in FIG. 34 ,the crosslinked polythioester contains a thioester linkage in each ofits repeating units, which is covalently stable in neutral or slightlyacidic conditions. However, with the presence of excess PETMP, thethiol-thioester exchange reaction occurred rapidly only when accompaniedby simultaneous addition of a catalytic amount of triethylamine. Acetonein equivalent mass to nonvolatile compounds was added to improve themass transfer of solid/liquid phases. The film disappeared completely,and a colorless non-viscous solution of dissolved oligomers wasobtained. The devolatilized solution gives a viscous liquid, to which astoichiometric (thiol:ene) amount of TEDAE is added and directlyrepolymerized by a thiol-ene reaction. Three rounds of such operationswere conducted without noticeable changes in the properties of botholigomers and polymers. FIG. 35A shows that both the pristine andreclaimed polymers have a consistent glass transition temperature of −2°C., as well as a rubbery modulus of 6 MPa. Further, tensile tests showthose polymers break at ˜15% strain on average and a Young's modulus of˜8 MPa, as shown in FIG. 35B. Both pristine and recycled polymers arecolorless and transparent, as shown in FIG. 35C.

Example 13: Degradation and Recycling Using Various OligomerCompositions

Systematic study of both the degradation and repolymerization processwas then explored. The equilibrated balance between thiols andthioesters enables polythioesters to remain at thermodynamicallyminimized states, which are independent of the reaction route used toincorporate them into the polymer. A thiol-excess off-stoichiometricpolymer formed from PETMP and TEDAE, has the same molecular topology asa stoichiometric polymer that has exchanged with the same excess amountof thiols. Based on the Flory-Stockmayer equation, networks are formedfrom tetra-thiol/di-ene monomers with no higher than two molarequivalents of extra thiol groups (i.e., the off-stoichiometric ratio rmust be no less than 0.333). To avoid oligomers that are too viscous tohandle, a series of formulations with five, seven and nine molarequivalents of thiols were designed, in which the ene:thiolstoichiometric ratios are 0.167, 0.125 and 0.100, respectively, aslisted in Table 1.

In each round of degradation, the polymer samples disappeared withinthree hours and the solvent removed oligomers were of consistentviscosity. From oligomer 1, 2 and 3, the larger off-stoichiometric ratioled to lower molecular weight oligomeric molecules, which exhibiteddecreased viscosities from 3.2, 2.2 and 1.2 Pa·s, decreasing as thestoichiometric ratio increased. As shown in FIG. 36 , the thiol groupsin the oligomers were confirmed by FT-IR spectra. Further, the chemicalstructures were consistent between recycling rounds, which was confirmedby both ¹H NMR (FIG. 37A) and GPC (FIG. 37B). The expected typical Florydistribution was observed for the oligomers, where the fraction ofhigher molecular weight components decreased exponentially, as expectedfor step-growth polymers/oligomers formed at relatively low conversions.

TABLE 1 Formulations consisting of recycled thioester containing thiololigomers degrading PETMP-TEDAE polymers in an excess of PETMP. Sampleswere mixed with particular multiple equivalencies of thiol monomers, anequal mass of acetone and 20 wt % of TEA with respect to the total ofnonvolatile compounds, at ambient for 3 h. Ratio of Stoichiometricfunctionality Oligomer Entry number thiol:thioester Viscosity/Pa · sOligomer 1 0.167 10 1.2 ± 0.1 Oligomer 2 0.125 14 2.2 ± 0.2 Oligomer 30.1 18 3.2 ± 0.2

Example 14: Degradation and Recycling Polymerization Kinetics

The reaction kinetics were studied by monitoring the decrease ofreactive functionalities in real-time FT-IR. As shown in FIG. 38 , undermild irradiation conditions (5 mW/cm² @365 nm) the thiol-allyl etherpolymerizations occurred very rapidly. More than 90% conversion wasachieved within 3-5 seconds under very mild initiation conditions,during which one or two FT-IR scans were acquired. A kinetic profile wasobserved by overlaying many oligomer formulations together with thepristine sample, which indicated the consistency in reaction rates. ThePETMP-TEDAE system produced rubbery materials, thus the absence ofvitrification allowed a constant reaction rate, even from monomers withvarious viscosities.

Example 15: Recycled Polymer Stability Testing

PETMP and TEDAE are both aliphatic ester based monomers, which givehydrophobic polymers. By immersing the polymer samples in deionizedwater and examining the sample mass change over time, a stability testwas performed to examine stability relative to a control sample whichwas polymerized from stoichiometric PETMP and diallyl adipate. As listedin Table 2, no substantial difference was seen between the polythioesterand the control group, indicating the durability of recyclable thioestercontaining polymers. Further, thermal stability was demonstrated as nodetectable weight loss was observed up to 320° C. under N₂, as shown inFIG. 39 . Though extremely dynamic under exchange conditions, thethioester groups bring no discernable harm to the stability anddurability over solvent and heat.

TABLE 2 Water swelling and stability tests in neutral deionized water atambient temperature. The thioester film was prepared from stoichiometricPETMP and TEDAE, while the control film was made from stoichiometricPETMP and diallyl adipate. Weight change Weight change Weight change 1day 3 days 1 week Thioester film 0.9% (±0.1%) 0.8% (±0.1%) 0.7% (±0.1%)Control film 0.8% (±0.1%) 0.8% (±0.1%) 0.6% (±0.1%)

Example 16: Tunability of Recyclable Polymers

In step-growth reactions, the network structures are readily adjustableby simple changes to the monomer structures, and thus, materialproperties are precisely tunable. Polymers comprising various thiolmonomers (FIG. 40 ) polymerized with stoichiometric TEDAE weresynthesized (Table 3). Both chemical structure and functionality of thethiol monomers were found to affect the polymer properties. Structurallysimilar tri-thiol (TMPTMP), tetra-thiol (PETMP) and hexa-thiol(Di-PETMP)monomers generated polymers with small increases in Tg going from −4 to−2 to 7, with rubbery moduli of 3.5, 6.0 and 8.6 MPa, respectively. Thetri-thiol with a stiff ring-structured core (TEMPIC) generated anincreased Tg as compared to that of TMPTMP, while the flexiblepolyethylene glycol based thiols (ETTMP 700 and 1300) generated softermaterials. After degradation by exchange with the respective thiolmonomers, the oligomers were recovered (NMR spectra of oligomers areshown in FIG. 41 ). The viscosity of the oligomers varied predictably inregards to the respective monomer structures. For example, the TEMPIColigomer had a viscosity of 108 Pas while the ETTMP oligomers had aviscosity of 1 Pas. By altering one of the two reactive components, itwas possible to design recyclable thiol-ene polymers for a range ofparticular material applications.

TABLE 3 Formulations of recyclable polymers prepared by various thiolmonomers with TEDAE. Recycled Rubbery Recycling oligomer Thiol modulus/stoichiometry viscosity/ monomers Tg/° C. MPa ratio ene:thiol Pa · sTri-thiol TMPTMP −4 3.5 0.25 4.1 ± 0.2 TEMPIC 6 1.7 0.25 108 ± 4  ETTMP700 −22 1.8 0.25 1.4 ± 0.1 ETTMP1300 −28 1.3 0.25 1.8 ± 0.1Tetra-thiol PETMP −2 6.0 0.167 11 ± 1  PCL4SH −23 2.4 0.167 3.8 ± 0.1Hex-thiol Di-PETMP 7 8.6 0.1 32 ± 2 

Example 17: Thiol-Isocyanate Glassy Recyclable Polymers

Irgacure 907 was used as a photolabile base to photopolymerize PETMPwith a thioester containing di-isocyanate monomer (TEDI). Thepolymerization occured rapidly under mild irradiation conditions (5mW/cm² @365 nm, FIG. 42 ) but slowed down as the polymer vitrified. Thereaction conversion was limited at ˜70% conversion but the reaction wasfully completed when post-curing at 80° C., as confirmed by FT-IRspectra (FIG. 43 ). Degraded oligomers were obtained by exchanging withextra PETMP under similar conditions as those reported in Examples11-13. The pristine isocyanate containing polymer showed a Tg of 74° C.,while the reclaimed polythiourethanes have a Tg of 73° C., as verifiedby DMA (FIG. 44 ). Both pristine and reclaimed polymers had a rubberymodulus of approximately 9 MPa, indicating nearly identical networkstructures. Further, the tensile test showed that the Young's moduluswas close to 1.5 GPa (FIG. 45 ), which is suitable for applications suchas hard coatings.

Example 18: Anionic Mediated Disulfide Exchange Reactions for theRecycling of Thiol-Ene Photopolymers

A disulfide containing diallyl ether monomer (DSDAE) was synthesized byFisher esterification between 3,3′-dithiodipropionic acid and allylalcohol. Stoichiometric PETMP-DSDAE with 1 mol % Irgacure 184 as thephotoinitiator yielded transparent, tack-free, crosslinked polymersafter 10 min of UV irradiation. Similar to the thioester system, thedisulfide polymer completely degraded into oligomers in the presence ofexcess PETMP (stoichiometric number of 0.125) and catalytic amount ofTEA in acetone after reacting overnight. The reclaimed disulfide polymerpossessed nearly identical mechanical properties as the pristinesamples, with a Tg of −6° C. and a rubbery modulus of 9 MPa (FIG. 46 ).Further, the reaction kinetics of the recycled polymer and the pristinepolymer were found to be identical. As shown in FIG. 47 , both thepristine and the recycled systems demonstrated a rapid reaction rate,reaching full conversion in a thiol/ene stoichiometric manner within 10mins of irradiation.

Example 19: Silica Particle-Polymer Composites

Filler-reinforced composites are commonly employed with photopolymers inorder to obtain enhanced mechanical properties, including increasedtensile modulus. PETMP-TEDAE polymers loaded with various amount ofsilica particles (diameter 0.4 μm) were prepared, and their compositionswere confirmed by TGA analysis (FIG. 48 ). Samples loaded with 50 wt %and 60 wt % particles showed weight losses of 50% and 40%, respectively.The rubbery modulus of 50 wt % and 60 wt % particle loading compositeswere found to be 94 MPa and 282 MPa, respectively, both of which weresignificantly higher than the pure PETMP-TEDAE polymer (6 MPa), as shownin FIG. 49 . The composites degraded completely under the sameconditions as the neat polymer, and both silica particles and thiololigomers were recovered by centrifugation and subsequent drying undervacuum.

Example 20: Photolithography Applications of Recyclable Polymers

As shown in FIGS. 50A and 50B, both pristine and recycled PETMP-TEDAEpolymers were prepared as cylinders with 100 μm in diameter and 80 μm inheight, on glass slides. The recycled samples required less curing timethan pristine samples as a result, potentially due to the increasedviscosity. Both of the surface features were degradable under similarconditions as the bulk films. This implementation in photolithography,can be used in fabricating materials such as optical devices, functionalsurfaces and 3D objects.

Example 21: Shrinkage Stress Test

Polymerization induced stress was measured for a thioester polymernetwork (bottom line) comprising TEDAE (1.0 eq), PETMP (1.1 eq) and TMG(0.03 eq) and a control polymer network (top line) comprising DAEC (1.0eq), PETMP (1.1 eq) and TMG (0.03 eq) (FIG. 51 ). In situ polymerizationshrinkage stress measurements were performed utilizing a tensometer(American Dental Association Health Foundation, ADAHF-PRC). Briefly,samples were placed between two silanized glass rods (6 mm in diameter,1 mm in thickness). During the measurement, tensile force generated bybonded shrinking led to a deflection of the cantilever beam. Thisdeflection was measured by a linear variable differential transformer(LVDT) and then converted to force based on a beam calibration constant.Shrinkage stress was calculated using the deflection force divided bythe cross-sectional sample area. The simultaneous conversion measurementwas recorded by the FTIR spectrometer connected via fiber optic cables.Samples were irradiated for 100 s (365 nm 30 mW cm⁻²). Shrinkage stresswas monitored for 8 minutes after the light source was switched off toobtain the final shrinkage stress at ambient temperature. The TEDAEcontaining network demonstrated a lower ultimate stress and continued todecrease over time. The control (DAEC) network reached a higher ultimatestress and did not decrease over time.

The disclosures of each and every patent, patent application, andpublication cited herein are hereby incorporated herein by reference intheir entirety. While this invention has been disclosed with referenceto specific embodiments, it is apparent that other embodiments andvariations of this invention may be devised by others skilled in the artwithout departing from the true spirit and scope of the invention. Theappended claims are intended to be construed to include all suchembodiments and equivalent variations.

1. A composition comprising: (a) at least one multifunctional thioestercontaining monomer of Formula (I): wherein in (I):

A¹ and A² are each independently selected from the group consisting ofoptionally substituted C₁-C₁₅ alkylene, optionally substituted C₂-C₁₅alkenylene, optionally substituted C₂-C₁₅ alkynylene, optionallysubstituted C₁₂-C₁₅ heteroalkylene, optionally substituted C₂-C₁₅heteroalkenylene, and optionally substituted C₂-C₁₅ heteroalkynylene; E¹and E² are each independently selected from the group consisting of:

wherein each instance of Y¹ is independently selected from the groupconsisting of O and NR¹; and each instance of R¹ being independentlyselected from the group consisting of H and C₁-C₆ alkyl; m1 is 0 or 1;m2 is 0 or 1; X¹ is

 wherein: bond a is to A¹, bond b is to E¹, Q is CH₂ or

 and n is 0, 1, 2, 3, 4, 5, or 6; X² is

 wherein: bond a is to A², bond b is to E², Q is CH₂ or

 and n is 0, 1, 2, 3, 4, 5, or 6; each instance of Y², and Y³ isindependently selected from the group consisting of CR¹ ₂, O and NR¹;and each instance of R¹ is independently selected from the groupconsisting of H and C₁-C₆ alkyl; (b) at least one multifunctional thiolmonomer; (c) at least one selected from the group consisting of a baseand a nucleophile; (d) optionally an acid selected from the groupconsisting of a photo-activatable acid and a thermal-activatable acid.2. The composition of claim 1, wherein the at least one multifunctionalthioester containing monomer is a monomer of Formula (Ia):


3. The composition of claim 1, wherein the at least one multifunctionalthioester containing monomer is selected from the group consisting of:

wherein each occurrence of m is independently selected from the groupconsisting of 0, 1, 2, 3, 4, 5, and
 6. 4. The composition of claim 1,wherein the at least one multifunctional thiol monomer is selected fromthe group consisting of: pentaerythritol tetramercaptopropionate(PETMP); ethylene glycol bis(3-mercaptopropionate) (EGBMP);trimethylolpropane tris(3-mercaptopropionate)(TMPMP);2,4,6-trioxo-1,3,5-triazina-triy (triethyl-tris (3-mercapto propionate);1,2-ethanedithiol; 1,3-propanedithiol; 1,4-butanedithiol;1,5-pentanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol;1,9-nonanedithiol; 1,11-undecanedithiol; 1,16-hexadecanedithiol;2,5-dimercaptomethyl-1,4-dithiane; pentaerythritol tetramercaptoacetate;trimethylolpropane trimercaptoacetate; glycol dimercaptoacetate;2,3-dimercapto-1-propanol; DL-dithiothreitol; 2-mercaptoethylsulfide;2,3-(dimercaptoethylthio)-1-mercaptopropane; 1,2,3-trimercaptopropane;toluenedithiol; benzenedithiol; biphenyldithiol; benzenedimethanethiol;xylylenedithiol; 4,4′-dimercaptostilbene; glycol dimercaptopropionate;

wherein each instance of n is independently an integer from 0 to 500.5-6. (canceled)
 7. The composition of claim 1, wherein the base has aconjugate acid with a pKa from about 2 to about 15, or wherein thenucleophile has a nucleophilicity value (N) greater than about
 10. 8.(canceled)
 9. The composition of claim 1, wherein at least one applies:(a) the base is selected from the group consisting of an alkylthiolatesalt, tetramethylguanidine (TMG), 1,8-Diazabicyclo[5,4,0]undec-7-ene(DBU), N,N-Diisopropylethylamine (DIPEA or Hunig's base), 4-tert-butylpyridine, triethylamine (TEA), andN,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA); (b) the nucleophileis selected from the group consisting of quinuclidine,1,4-diazabicyclo[2.2.2]octane (DABCO), 4-Dimethylaminopyridine (DMAP),IMes, IPr, Ender's carbene, PPh₃ P(nBu), P(tBu), PCy₃, and PMe₃. 10-11.(canceled)
 12. The composition of claim 1, further comprising at leastone polymerization initiator selected from the group consisting of aphotoinitiator, a thermal initiator, and a redox initiator. 13.(canceled)
 14. The composition of claim 12, wherein at least oneapplies: (a) the at least one photoinitiator is selected from the groupconsisting of: acetophenone, benzophenone, 2-phenylacetophenone,2,2-dimethoxy-2-phenylacetophenone,Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone,2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one,Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Ethyl(2,4,6-trimethylbenzoyl) phenyl phosphinate, lithiumphenyl-2,4,6-trimethylbenzoylphosphinate,

(b) the at least one thermal initiator is a compound selected from thegroup consisting of tert-Amyl peroxybenzoate, 4,4-Azobis(4-cyanovalericacid), 1,1′-Azobis(cyclohexanecarbonitrile), 2,2′-Azobisisobutyronitrile(AIBN), Benzoyl peroxide, 2,2-Bis(tert-butylperoxy)butane,1,1-Bis(tert-butylperoxy)cyclohexane,2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane,2,5-Bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,Bis(1-(tert-butylperoxy)-1-methylethyl)benzene,1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-Butylhydroperoxide, tert-Butyl peracetate, tert-Butyl peroxide, tert-Butylperoxybenzoate, tert-Butylperoxy isopropyl carbonate, cumenehydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroylperoxide, 2,4-pentanedione peroxide, peracetic acid, and potassiumpersulfate; (c) the at least one redox initiator is selected from thegroup consisting of: sodium iodide/hydrogen peroxide, potassiumiodide/hydrogen peroxide, benzoyl peroxide/dimethyaniline, benzoylperoxide/N,N-dimethyl p-toluidine, benzoylperoxide/4-N,N-dimethylaminophenethyl alcohol, benzoyl peroxide/ethyl4-dimethylamino benzoate, glucose oxidase/oxygen/iron(II) sulfate; andcopper(II) sulfate/sodium ascorbate. 15-17. (canceled)
 18. Thecomposition of claim 1, wherein the relative ratio between the at leastone multifunctional thioester containing monomer and the at least onemultifunctional thiol monomer in a such that the total number of thiolfunctionalities present on the at least one multifunctional thiolmonomer within the composition is greater than the total number of E¹and E² functionalities present on the at least one multifunctionalthioester containing monomer.
 19. The composition of claim 1, whereinthe base is selected from the group consisting of a photo-activatablebase and a thermal-activatable base.
 20. The composition of claim 19,wherein at least one applies: (a) the photo-activatable base is acompound selected from the group consisting of:

 1,2-Diisopropyl-3-[Bis (dimethylamino) methylene]guanidium2-(3-benzoylphenyl)propionate, 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, and (Z)-{[Bis(dimethylamino)methylidene] amino}-N-cyclohexyl(cyclohexylamino)methaniminiumtetrakis(3-fluorophenyl)borate; (b) the base is a thermal-activatablebase selected from the group consisting of:

(c) the photo-activatable acid is a compound selected from the groupconsisting of:

 Bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate,Bis(4-tert-butylphenyl)iodonium p-toluenesulfonate,Bis(4-tert-butylphenyl)iodonium, Boc-methoxyphenyldiphenylsulfoniumtriflate, (4-tert-Butylphenyl)diphenylsulfonium triflate,Diphenyliodonium hexafluorophosphate, Diphenyliodonium nitrate,Diphenyliodonium perfluoro-1-butanesulfonate, Diphenyliodoniump-toluenesulfonate, Diphenyliodonium triflate,(4-Fluorophenyl)diphenylsulfonium triflate, N-Hydroxynaphthalimidetriflate, N-Hydroxy-5-norbornene-2,3-dicarboximideperfluoro-1-butanesulfonate, (4-Iodophenyl)diphenylsulfonium triflate,(4-Methoxyphenyl)diphenylsulfonium triflate,2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,(4-Methylphenyl)diphenylsulfonium triflate, (4-Methylthiophenyl)methylphenyl sulfonium triflate, (4-Phenoxyphenyl)diphenylsulfonium triflate,(4-Phenylthiophenyl) diphenylsulfonium triflate, Triarylsulfoniumhexafluorophosphate salts, Triphenylsulfoniumperfluoro-1-butanesufonate, Triphenylsulfonium triflate,Tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate, andTris(4-tert-butylphenyl)sulfonium triflate; (d) the thermal-activatableacid is selected from the group consisting of


21. (canceled)
 22. The composition of claim 19, wherein the monomersundergo at least partial polymerization to form a covalent adaptablenetwork (CAN) polymer, wherein the CAN polymer does not exhibitsignificant bond exchange before activation of the base, and wherein theCAN polymer exhibits bond exchange after activation of the base. 23-27.(canceled)
 28. The composition of claim 1, wherein at least a fractionof the monomers undergo polymerization to form a CAN polymer.
 29. Thecomposition of claim 1, wherein the CAN polymer exhibits bond exchangebefore activation of the acid and wherein the CAN does not exhibitsignificant bond exchange after activation of the acid. 30.-51.(canceled)